CN108993466A - A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ - Google Patents
A kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ Download PDFInfo
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- CN108993466A CN108993466A CN201810893132.XA CN201810893132A CN108993466A CN 108993466 A CN108993466 A CN 108993466A CN 201810893132 A CN201810893132 A CN 201810893132A CN 108993466 A CN108993466 A CN 108993466A
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- dimensional ordered
- titanate
- ordered macroporous
- colloidal crystal
- crystal template
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000011065 in-situ storage Methods 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 115
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 129
- 239000004793 Polystyrene Substances 0.000 claims description 90
- 229920002223 polystyrene Polymers 0.000 claims description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- 235000019441 ethanol Nutrition 0.000 claims description 47
- 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 37
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 239000004005 microsphere Substances 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 238000011049 filling Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 131
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000523 sample Substances 0.000 description 32
- 229960004756 ethanol Drugs 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 16
- 229910052712 strontium Inorganic materials 0.000 description 16
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000001879 gelation Methods 0.000 description 14
- 238000004321 preservation Methods 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 11
- 241000790917 Dioxys <bee> Species 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000004038 photonic crystal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- -1 titanium Ester Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The present invention provides a kind of three-dimensional ordered macroporous titanate and its sacrifice preparation method certainly in situ, comprising: step 1, prepares mono-dispersion microballoon colloidal crystal template；Step 2, preparing titanium dioxide presoma；Step 3, colloidal crystal template is added in TiO 2 precursor, is placed under vacuum condition and impregnates, takes out and filter, stood；Step 4, the colloidal crystal template that will be filled with TiO 2 precursor is calcined in air atmosphere, obtains three-dimensional ordered macroporous titanium dioxide；Step 5, three-dimensional ordered macroporous titanium dioxide is placed in the metal ion solution for showing alkalinity, three-dimensional ordered macroporous titanate is obtained by hydro-thermal reaction.The present invention first prepares three-dimensional ordered macroporous titanium dioxide, three-dimensional ordered macroporous titanate is converted by three-dimensional ordered macroporous titanium dioxide again, avoid the process of synthesizing titanate precursor solution, it is low to overcome titanate precursor solution viscosity, is easy to cause the disadvantages of filling rate is low, material pore structure is imperfect, product shrinking percentage is larger.
Description
Technical field
The invention belongs to nanometer material science and photocatalysis chemical fields, and in particular to a kind of three-dimensional ordered macroporous titanate
And its it is in situ from sacrifice preparation method.
Background technique
With the development of society, the consumption of fossil energy increasingly increases severely, to people while bringing convenience to people's life
The environment that class is depended on for existence causes serious pollution, such as nitrogen oxides (NOx), sulfide (SOx), the volatile organics gas such as VOC
A large amount of exhaust emission atmospheric environments of body, endanger human health.With the development of photocatalysis technology, photocatalysis technology has become ring
One of border reparation, the effective means of water air cleaning.
There-dimensional ordered macroporous materials become the research hotspot of field of novel with its unique advantage, three-dimensional ordered macroporous
Material have photonic crystal characteristic, there are forbidden photon bands, and will appear slower rays area near photon band gap, when transmitted through light
When son meets this frequency, group velocity be will be greatly reduced, and become slower rays.If the frequency of slower rays and the light absorption of catalyst
The frequency in region coincides, and will enhance the extent of reaction of photon and material, increases the quantity of the electrons and holes in reaction, will
Absorption of the catalyst to light can significantly be promoted.It on the other hand is three-dimensional ordered macroporous structure compared to traditional film or block
With special curved-surface structure, is conducive to more reactants and is adsorbed in catalyst surface；Bigger pore volume is conducive to
Substance is spread rapidly in light-catalyzed reaction, due to the sky between each air balls of three-dimensional ordered macroporous structure there are also interior connection
Stomata can be such that the reactant in light-catalyzed reaction transports in the catalyst with product and become easier to, and tie better than common hole
Structure；Three-dimensional hole configurations can increase visible light scattering, and Multiple Scattering increases light path to light in the structure, enhance photon and material
The extent of reaction, more effectively improve photocatalysis efficiency.
Perofskite type oxide, such as titanate (XTiO3), with its flexible chemical composition, constituent content abundant and steady
Fixed structure becomes important functional material, research shows that titanate becomes one kind because of the strong ligand binding affinity of its alkali metal element
Adsoption catalysis material, XTiO3The basic site on surface is to acid contaminant gas (such as NOx) absorption conversion have it is very favorable
It influences.Current three-dimensional ordered macroporous XTiO3The report of material is seldom, document (Kai.Y, et al.Applied catalysis
B:environmental, 200 (2017) 514-520) three-dimensional ordered macroporous SrTiO is reported for the first time3Material is prepared first
Precursor solution, is then immersed the gap of template by strontium titanates precursor solution, and final calcining obtains three-dimensional ordered macroporous
SrTiO3.The Chinese invention patent document of Publication No. CN107973339A discloses a kind of three-dimensional order that porous nano-sheet is constructed
Macropore calcium titanate photonic crystal and its synthetic method, method is also first to configure calcium titanate precursor solution, then by presoma
Solution immerses the gap of template, and final calcining obtains three-dimensional ordered macroporous CaTiO3.Titanate does not have direct predecessor, needs
Precursor solution is prepared by chemical synthesis, and the precursor solution concentration configured is low, viscosity is small；Precursor solution immerses mould
When plate gap, it is easy to cause filling rate low, the pore structure of material is imperfect, and product shrinking percentage is larger.
Summary of the invention
In view of the problems of the existing technology, the object of the present invention is to provide a kind of three-dimensional ordered macroporous titanate and its originals
Position avoids the process of synthesizing titanate precursor solution, overcomes titanate precursor solution viscosity from preparation method is sacrificed
It is low, it is easy to cause the disadvantages of filling rate is low, material pore structure is imperfect, product shrinking percentage is larger.
The present invention is to be achieved through the following technical solutions:
The method for preparing three-dimensional ordered macroporous titanate is sacrificed in a kind of original position certainly, first prepares three-dimensional ordered macroporous titanium dioxide
Titanium, then three-dimensional ordered macroporous titanium dioxide and salting liquid are prepared into three-dimensional ordered macroporous titanate by hydro-thermal reaction.
Preferably, specifically comprise the following steps,
Step 1, mono-dispersion microballoon colloidal crystal template is prepared；
Step 2, preparing titanium dioxide presoma；
Step 3, colloidal crystal template is added in TiO 2 precursor, and is placed under vacuum condition and impregnates, taken
It out and filters, stands；
Step 4, the colloidal crystal template filled with TiO 2 precursor step 3 obtained is forged in air atmosphere
It burns, obtains three-dimensional ordered macroporous titanium dioxide；
Step 5, three-dimensional ordered macroporous titanium dioxide is placed in the metal ion solution for showing alkalinity, and it is anti-to carry out hydro-thermal
It answers, product is washed, dry to get three-dimensional ordered macroporous titanate.
Further, in step 1, mono-dispersion microballoon colloidal crystal template is polystyrene microsphere or poly-methyl methacrylate
The colloidal crystal template of ester microsphere preparation.
Further, in step 2, method particularly includes: titanium-containing compound is uniformly mixed to obtain titanium dioxide forerunner with alcohol
Body；Wherein, titanium-containing compound is one of butyl titanate, isopropyl titanate or titanium tetrachloride, titanium-containing compound and alcohol
Volume ratio is 1:(0-100).
Further, in step 2, the alcohol is one in methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol or cyclohexanol
Kind.
Further, it in step 3, before colloidal crystal template is placed in TiO 2 precursor, is first walked as follows
It is rapid: colloidal crystal template being soaked in alcohol, is placed under vacuum condition and keeps 1-180min；It then takes out and filters, it is described
Alcohol is one of methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol or cyclohexanol.
Further, in step 4, calcining is specifically to be warming up to 400-1000 DEG C with the heating rate of 0.1-50 DEG C/min,
Keep the temperature 0.5-24h.
Further, in step 5, the metal ion in metal ion solution is Sr2+、Ca2+、Ba2+、Co2+Or Mn2+In
One kind, the concentration of metal ion are 0.1-10000mM.
Preferably, in step 5, hydrothermal temperature is 80-250 DEG C, reaction time 0.1-100h.
A kind of three-dimensional ordered macroporous titanate, adopts and is prepared with the aforedescribed process.
Compared with prior art, the invention has the following beneficial technical effects:
Preparation method of the present invention first prepares three-dimensional ordered macroporous titanium dioxide using existing TiO 2 precursor
Titanium, then three-dimensional ordered macroporous titanate is prepared by hydro-thermal reaction, i.e., it is former by three-dimensional ordered macroporous titanium dioxide hydro-thermal reaction
Position prepares corresponding titanate from sacrifice；The process for preparing titanate precursor solution is avoided, and is overcome due to synthesis
Titanate precursor solution viscosity is low and is easy to cause filling rate is low, material pore structure is imperfect, product shrinking percentage is larger etc.
Disadvantage.Meanwhile obtain by the method for the invention be titanium dioxide and titanate heterojunction material, photo-generated carrier can be promoted
Separative efficiency, and then improve photochemical catalyst catalytic performance.Preparation method of the present invention can prepare work with save the cost and time
Skill is simple, low for equipment requirements.The present invention has very big application value in terms of actual air purification and wastewater treatment.
Further, first colloidal crystal template is soaked in alcohol, due to alcohol good fluidity, easily enters colloidal crystal mould
Plate gap, so that the duct of colloidal crystal template be made to infiltrate, then when colloidal crystal template is soaked in TiO 2 precursor,
Alcohol plays drainage, so that TiO 2 precursor is just easier to enter colloidal crystal template gap.
Further, three-dimensional ordered macroporous titanate not only can be obtained in the present invention, but also can pass through control hydro-thermal reaction
The parameters such as temperature, time and concentration of metal ions accurately control the two-phase proportion of titanium dioxide and titanate, directly construct corresponding
Heterojunction material.
The material filling rate that the present invention is prepared is high, pore structure is complete, shrinking percentage is small；And it obtains being titanium dioxide
With the heterojunction material of titanate, the separative efficiency of photo-generated carrier can be promoted, and then improves the catalytic performance of photochemical catalyst.
Detailed description of the invention
Fig. 1 is PS colloidal crystal template SEM figure prepared by the embodiment of the present invention 1；
Fig. 2 is that three-dimensional ordered macroporous strontium titanates prepared by the embodiment of the present invention 1 is fast to the degradation of NO under simulated solar irradiation
Rate curve graph；
Fig. 3 is the XRD diagram of three-dimensional ordered macroporous strontium titanates prepared by the embodiment of the present invention 2；
Fig. 4 is the SEM figure of three-dimensional ordered macroporous strontium titanates prepared by the embodiment of the present invention 2；
Fig. 5 is the ultraviolet-visible diffuse reflectance spectrum figure of three-dimensional ordered macroporous strontium titanates prepared by the embodiment of the present invention 2.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Thinking of the invention is: there are direct presoma (such as tetraisopropyl titanates, four fourth of metatitanic acid for the metal oxide of titanium
Ester), disadvantage brought by synthesizing titanate presoma can be overcome with its directly filling microballoon colloidal crystal template, obtained final
The three-dimensional ordered macroporous titanium dioxide arrived is in situ to obtain corresponding XTiO from sacrifice by hydro-thermal method3.Three not only can be obtained in this way
Ordered big hole titanate is tieed up, can also accurately control two by parameters such as temperature, time and the cation concns of control hydro-thermal reaction
Phase Proportion directly constructs corresponding heterojunction material, can promote the separative efficiency of photo-generated carrier, and then improve photochemical catalyst
Catalytic performance.
The method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position of the present invention certainly, specifically includes:
(1) mono-dispersion microballoon colloidal crystal template is prepared；
(2) titanium-containing compound is uniformly mixed according to a certain volume to obtain solution A with alcohol；
(3) colloidal crystal template is first soaked in alcohol, is placed in vacuum oven, protected under certain vacuum degree
Hold 1-180min；Be then taken out and filter out alcohol, immediately will be filled with alcoholic solution colloidal crystal template be placed in it is molten
It in liquid A, is equally placed on keeping 1-180min in vacuum oven and under certain vacuum degree, finally be drawn off and mistake
Solution A is filtered, the colloidal crystal template that will be filled with solution A places 0.5-100h at room temperature；Preferably, described certain true
The reciprocal of duty cycle lower retention time is 5-100min.
(4) colloidal crystal template filled with solution A that step (3) obtains is calcined in air atmosphere, with 0.1-50
DEG C/heating rate of min is warming up to 400-1000 DEG C, 0.5-24h is kept the temperature, three-dimensional ordered macroporous titanium dioxide is finally obtained；
(5) three-dimensional ordered macroporous titanium dioxide is placed in hydro-thermal reaction certain time in the metal ion solution for showing alkalinity,
Hydro-thermal finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dry sample has to get three-dimensional
Sequence macropore titanate.
In step (1), the microballoon in the mono-dispersion microballoon colloidal crystal template can be polystyrene (PS) microballoon or poly-
Methyl methacrylate (PMMA) microballoon.
In step (2), the titanium-containing compound is one of butyl titanate, isopropyl titanate or titanium tetrachloride, is contained
The volume ratio of titanium compound and alcohol is 1:(0-100)；Preferably, the titanium-containing compound is isopropyl titanate.
In step (2), the alcohol is selected from one of methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol or cyclohexanol, makees
To be preferred, the alcohol is ethyl alcohol, and ethyl alcohol is most universal and common alcoholic solvent, cheap, non-toxic.
In step (3), the alcohol is selected from one of methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol or cyclohexanol, makees
To be preferred, the alcohol is methanol, and methanol molecules amount is minimum, and good fluidity easily enters stencil apertures.Methanol is first used in this step
Then the gap of solution filling template refills corresponding presoma, can play drainage because being filled in the methanol of stencil apertures
Effect can make presoma be easier to enter stencil apertures.
In step (3), the vacuum degree is 113Pa-60.133Kpa.
In step (5), the metal ion solution of the aobvious alkalinity is the pH that metal ion solution is adjusted by sodium hydroxide
For 9-14.
In step (5), the metal ion includes Sr2+、Ca2+、Ba2+、Co2+Or Mn2+One of, metal ion
Concentration is 0.1-10000mM.Metal ion is introduced by its corresponding metal salt, and metal salt is nitrate or chlorate.
In step (5), the hydrothermal temperature is 80-250 DEG C, reaction time 0.1-100h, preferably, reaction
Time is 0.3-72h.
Specific embodiment is as follows.
Embodiment 1
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) isopropyl titanate is used directly as solution A；
(3) PS colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum degree
20.133kPa lower holding 20min；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template is placed in solution A, is equally placed in vacuum oven and is kept at vacuum degree 20.133kPa
30min is finally drawn off and filters out isopropyl titanate, will be filled with the PS colloidal crystal template of isopropyl titanate in room temperature
Lower placement 12h makes the precursor solution isopropyl titanate in structure hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 1 DEG C/min
550 DEG C of heat preservation 3h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 33mM is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous two
Titanium oxide is added in the metal ion solution of this alkalinity and is transferred to autoclave together, the hydro-thermal reaction 90min at 180 DEG C,
Hydro-thermal finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, obtains three-dimensional order
Macropore strontium titanates.
PS colloidal crystal template manufactured in the present embodiment characterizes its pattern, SEM schemes as shown in Figure 1, PS glue
Body crystal template is arranged in hexagonal, forms the close-packed structure based on face-centered cubic (fcc).
Three-dimensional ordered macroporous strontium titanates manufactured in the present embodiment, the NO gas for being 400ppb by current system degradation concentration
Its photocatalysis effect is assessed, to the degradation rate curve graph of NO as shown in Fig. 2, curve A is sample under simulated solar irradiation
Degradation rate curve, Blank be blank sample, from figure we, it is apparent that after turning on light sample have to NO it is bright
Aobvious degradation, and reach balance after 5min, degradation efficiency is always held at 30% or more within 30min.
Embodiment 2
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) isopropyl titanate is used directly as solution A；
(3) PS colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum degree
20.133kPa lower holding 20min；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template is placed in isopropyl titanate solution, is equally placed in vacuum oven and in vacuum degree
20min is kept under 20.133kPa, is finally drawn off and filters out isopropyl titanate, will be filled with the colloid of isopropyl titanate
Crystal template places 12h at room temperature, and the precursor solution in structure is made to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 1 DEG C/min
550 DEG C of heat preservation 3h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 33mM is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous two
Titanium oxide is added in the metal ion solution of this alkalinity and is transferred to autoclave together, the hydro-thermal reaction 30min at 180 DEG C,
Hydro-thermal finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, obtains three-dimensional order
Macropore strontium titanates.
Three-dimensional ordered macroporous strontium titanates manufactured in the present embodiment characterizes its crystal structure with XRD, XRD diffraction
Figure is as shown in figure 3, obtaining product is titanium dioxide and strontium titanates heterojunction material.
Three-dimensional ordered macroporous strontium titanates pattern manufactured in the present embodiment is characterized, SEM figure is as shown in figure 4, can be with
The aperture for finding out to obtain material is uniform, and substantially all in 120nm or so, pore structure is basic complete and blocks or breaks without apparent aperture
Damage phenomenon.
Three-dimensional ordered macroporous strontium titanates optical characteristics manufactured in the present embodiment is characterized, UV-Vis DRS
Spectrum is as shown in figure 5, from figure this it appears that the photonic crystal properties of There-dimensional ordered macroporous materials, forbidden photon band position exists
The place 400nm or so.
Embodiment 3
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) by tetraisopropyl titanate, 1:1 is mixed by volume with dehydrated alcohol, and magnetic agitation 30min obtains homogeneous solution
A；
(3) PS colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum degree
30.133kPa lower holding 30min；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template is placed in solution A, is equally placed in vacuum oven and is kept at vacuum degree 30.133kPa
30min is finally drawn off and filters out solution A, and the PS colloidal crystal template that will be filled with solution A is placed for 24 hours at room temperature,
The precursor solution in structure is set to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 5 DEG C/min
500 DEG C of heat preservation 6h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 3mM is prepared3)2Aqueous solution is 14 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 30h, hydro-thermal at 120 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Strontium titanates.
Embodiment 4
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) by tetraisopropyl titanate, 1:3 is mixed by volume with dehydrated alcohol, and magnetic agitation 10min obtains homogeneous solution
A；
(3) PS colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum degree
30.133kPa lower holding 40min；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template is placed in solution A, is equally placed in vacuum oven and is kept at vacuum degree 30.133kPa
40min is finally drawn off and filters out solution A, and the PS colloidal crystal template that will be filled with solution A is placed for 24 hours at room temperature,
The precursor solution in structure is set to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 10 DEG C/min
450 DEG C of heat preservation 6h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) CaCl of 1.3mM is prepared2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium be added this alkalinity metal ion solution in and be transferred to autoclave together, at 150 DEG C hydro-thermal reaction for 24 hours, hydro-thermal
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Calcium titanate.
Embodiment 5
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) by tetraisopropyl titanate, 1:6 is mixed by volume with dehydrated alcohol, and magnetic agitation 15min obtains homogeneous solution
A；
(3) PS colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum degree
30.133kPa lower holding 25min；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template is placed in solution A, is equally placed in vacuum oven and is kept at vacuum degree 30.133kPa
25min is finally drawn off and filters out solution A, and the colloidal crystal template that will be filled with solution A is placed for 24 hours at room temperature, makes
Precursor solution hydrolysis and gelation in structure；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 2 DEG C/min
450 DEG C of heat preservation 6h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) CaCl of 0.8mM is prepared2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 20min, water at 210 DEG C
Heat finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, it is big to obtain three-dimensional order
Hole calcium titanate.
Embodiment 6
(1) monodisperse PMMA microballoon is prepared using surfactant- free emulsion polymerization, is self-assembled into PMMA microsphere by being centrifuged
PMMA colloidal crystal template dries it at 70 DEG C；
(2) by butyl titanate, 1:1 is mixed by volume with dehydrated alcohol, and magnetic agitation 20min obtains homogeneous solution A；
(3) PMMA colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum
20min is kept under degree 10.133kPa；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PMMA colloidal crystal template be placed in solution A, be equally placed in vacuum oven and at vacuum degree 10.133kPa
20min is kept, is finally drawn off and filters out solution A, the colloidal crystal template that will be filled with solution A is placed at room temperature
40h makes the precursor solution in structure hydrolyze simultaneously gelation；
(4) the PMMA colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 5 DEG C/min
650 DEG C of heat preservation 4h remove PMMA colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) BaCl of 15mM is prepared2Aqueous solution is 12 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 48h, hydro-thermal at 120 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Barium titanate.
Embodiment 7
(1) monodisperse PMMA microballoon is prepared using surfactant- free emulsion polymerization, is self-assembled into PMMA microsphere by being centrifuged
PMMA colloidal crystal template dries it at 70 DEG C；
(2) by butyl titanate, 1:10 is mixed by volume with dehydrated alcohol, and magnetic agitation 20min obtains homogeneous solution
A；
(3) PMMA colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum
30min is kept under degree 10.133kPa；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PMMA colloidal crystal template be placed in solution A, be equally placed in vacuum oven and at vacuum degree 10.133kPa
30min is kept, is finally drawn off and filters out solution A, the colloidal crystal template that will be filled with solution A is placed at room temperature
12h makes the precursor solution in structure hydrolyze simultaneously gelation；
(4) the PMMA colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 2 DEG C/min
500 DEG C of heat preservation 8h remove PMMA colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) BaCl of 0.5mM is prepared2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 48h, hydro-thermal at 120 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Barium titanate.
Embodiment 8
(1) monodisperse PMMA microballoon is prepared using surfactant- free emulsion polymerization, is self-assembled into PMMA microsphere by being centrifuged
PMMA colloidal crystal template dries it at 70 DEG C；
(2) by butyl titanate, 1:10 is mixed by volume with dehydrated alcohol, and magnetic agitation 20min obtains homogeneous solution
A；
(3) PMMA colloidal crystal template is first soaked in methanol solution, is placed in vacuum oven, in vacuum
30min is kept under degree 35.133kPa；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PMMA colloidal crystal template be placed in solution A, be equally placed in vacuum oven and at vacuum degree 35.133kPa
30min is kept, is finally drawn off and filters out solution A, the colloidal crystal template that will be filled with solution A is placed at room temperature
12h makes the precursor solution in structure hydrolyze simultaneously gelation；
(4) the PMMA colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 6 DEG C/min
700 DEG C of heat preservation 2h remove PMMA colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) BaCl of 60mM is prepared2Aqueous solution is 11 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 48h, hydro-thermal at 100 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Barium titanate.
Embodiment 9
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) titanium tetrachloride is uniformly mixed according to volume ratio 1:30 with isopropanol and uses as solution A；
(3) PS colloidal crystal template is first soaked in aqueous isopropanol, is placed in vacuum oven, in vacuum
1min is kept under degree 133Pa；It is then taken out and is filtered out methanol solution, immediately will be filled with the PS glue of methanol solution
Body crystal template is placed in solution A, is equally placed in vacuum oven and is kept 1min at vacuum degree 133Pa, most
After be drawn off and filter out isopropyl titanate, the PS colloidal crystal template that will be filled with isopropyl titanate is placed at room temperature
5h makes the precursor solution isopropyl titanate in structure hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 0.1 DEG C/min
400 DEG C of heat preservations for 24 hours, remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Ba (NO of 0.1mM is prepared3)2Aqueous solution is 9 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous two
Titanium oxide is added in the metal ion solution of this alkalinity and is transferred to autoclave together, hydro-thermal reaction 55h, water at 100 DEG C
Heat finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, it is big to obtain three-dimensional order
Hole barium titanate.
Embodiment 10
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) isopropyl titanate is uniformly mixed according to volume ratio 1:60 with methanol and uses as solution A；
(3) PS colloidal crystal template is first soaked in ethanol solution, is placed in vacuum oven, in vacuum degree
1.133kPa lower holding 5min；It is then taken out and is filtered out methanol solution, immediately will be filled with the PS of methanol solution
Colloidal crystal template is placed in solution A, is equally placed in vacuum oven and is kept at vacuum degree 1.133kPa
5min is finally drawn off and filters out isopropyl titanate, will be filled with the PS colloidal crystal template of isopropyl titanate in room temperature
Lower placement 2h makes the precursor solution isopropyl titanate in structure hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 40 DEG C/min
800 DEG C of heat preservation 10h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) CoCl of 100mM is prepared2Aqueous solution is 10 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 100h, hydro-thermal at 80 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Cobalt titanate.
Embodiment 11
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) isopropyl titanate is uniformly mixed according to volume ratio 1:80 with n-butanol and uses as solution A；
(3) PS colloidal crystal template is first soaked in butanol solution, is placed in vacuum oven, in vacuum
100min is kept under degree 40.133kPa；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template be placed in solution A, be equally placed in vacuum oven and protected at vacuum degree 40.133kPa
100min is held, isopropyl titanate is finally drawn off and filters out, the PS colloidal crystal template that will be filled with isopropyl titanate exists
0.5h is placed at room temperature, and the precursor solution isopropyl titanate in structure is made to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 50 DEG C/min
1000 DEG C of heat preservation 8h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Mn (NO of 1M is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 30min, water at 200 DEG C
Heat finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, it is big to obtain three-dimensional order
Hole manganese titanate.
Embodiment 12
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) titanium tetrachloride is uniformly mixed according to volume ratio 1:100 with cyclohexanol and uses as solution A；
(3) PS colloidal crystal template is first soaked in hexamethylene alcoholic solution, is placed in vacuum oven, in vacuum
180min is kept under degree 60.133kPa；It is then taken out and is filtered out methanol solution, immediately will be filled with methanol solution
PS colloidal crystal template be placed in solution A, be equally placed in vacuum oven and protected at vacuum degree 60.133kPa
180min is held, isopropyl titanate is finally drawn off and filters out, the PS colloidal crystal template that will be filled with isopropyl titanate exists
50h is placed at room temperature, and the precursor solution isopropyl titanate in structure is made to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 1 DEG C/min
550 DEG C of heat preservation 3h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 5M is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 5min, hydro-thermal at 250 DEG C
It finishes, with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally sample is dried, is obtained three-dimensional ordered macroporous
Strontium titanates.
Embodiment 13
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 70 DEG C；
(2) isopropyl titanate is used directly as solution A；
(3) PS colloidal crystal template is placed in solution A, is placed in vacuum oven and in vacuum degree
180min is kept under 10.133kPa, is finally drawn off and filters out isopropyl titanate, will be filled with the PS glue of isopropyl titanate
Body crystal template places 100h at room temperature, and the precursor solution isopropyl titanate in structure is made to hydrolyze simultaneously gelation；
(4) the PS colloidal crystal template that will be filled with presoma is calcined in being placed in Muffle furnace, is warming up to 1 DEG C/min
550 DEG C of heat preservation 3h remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 10M is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous dioxy
Change titanium to be added in the metal ion solution of this alkalinity and be transferred to autoclave together, hydro-thermal reaction 90min, water at 180 DEG C
Heat finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, it is big to obtain three-dimensional order
Hole strontium titanates.
Embodiment 14
(1) Monodisperse Polystyrene Microspheres are prepared using dispersion copolymerization method, PS microballoon is self-assembled into PS colloidal crystal by being centrifuged
Template dries it at 60 DEG C；
It (2) is 10:2:5:4 preparing titanium dioxide precursor sol with volume ratio with ethyl alcohol, hydrochloric acid, isopropyl titanate, water,
It is used as Sol A；
(3) PS colloidal crystal template is placed in Sol A, is placed in vacuum oven and in vacuum degree
30min is kept under 10.133kPa, is finally drawn off and filters out Sol A, will be filled with the PS Colloidal crystals of TiO 2 sol
Body template places 100h at room temperature, makes sol-hydrolysis and gelation in structure；
(4) the PS colloidal crystal template that will be filled with colloidal sol is calcined in being placed in Muffle furnace, is warming up to 550 with 1 DEG C/min
DEG C heat preservation 3h, remove PS colloidal crystal template, finally obtain three-dimensional ordered macroporous titanium dioxide；
(5) Sr (NO of 10mM is prepared3)2Aqueous solution is 13 by the pH that NaOH adjusts solution, by three-dimensional ordered macroporous two
Titanium oxide is added in the metal ion solution of this alkalinity and is transferred to autoclave together, the hydro-thermal reaction 90min at 180 DEG C,
Hydro-thermal finishes, and with ethyl alcohol, deionized water cleaning sample to remove surface ion impurity, finally dries sample, obtains three-dimensional order
Macropore strontium titanates.
Claims (10)
1. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in a kind of original position certainly, which is characterized in that it is big first to prepare three-dimensional order
Porous titanium dioxide, then three-dimensional ordered macroporous titanium dioxide and salting liquid are prepared into three-dimensional ordered macroporous metatitanic acid by hydro-thermal reaction
Salt.
2. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 1 certainly, which is characterized in that tool
Body includes the following steps,
Step 1, mono-dispersion microballoon colloidal crystal template is prepared；
Step 2, preparing titanium dioxide presoma；
Step 3, colloidal crystal template is added in TiO 2 precursor, and is placed under vacuum condition and impregnates, taken out simultaneously
Filtering is stood；
Step 4, the colloidal crystal template filled with TiO 2 precursor step 3 obtained is calcined in air atmosphere, is obtained
To three-dimensional ordered macroporous titanium dioxide；
Step 5, three-dimensional ordered macroporous titanium dioxide is placed in the metal ion solution for showing alkalinity, and carries out hydro-thermal reaction, produced
Object is washed, dry to get three-dimensional ordered macroporous titanate.
3. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 2 certainly, which is characterized in that step
In rapid 1, mono-dispersion microballoon colloidal crystal template is Colloidal crystals prepared by polystyrene microsphere or poly (methyl methacrylate) micro-sphere
Body template.
4. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 2 certainly, which is characterized in that step
In rapid 2, method particularly includes: titanium-containing compound is uniformly mixed to obtain TiO 2 precursor with alcohol；Wherein, titanium-containing compound is
The volume ratio of one of butyl titanate, isopropyl titanate or titanium tetrachloride, titanium-containing compound and alcohol is 1:(0-100).
5. sacrificing the method for preparing three-dimensional ordered macroporous titanate, feature certainly according to the described in any item original positions of claim 4
It is, in step 2, the alcohol is one of methanol, ethyl alcohol, isopropanol, n-butanol, n-hexyl alcohol or cyclohexanol.
6. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 2 certainly, which is characterized in that step
In rapid 3, before colloidal crystal template is placed in TiO 2 precursor, first carries out following steps: colloidal crystal template is soaked
It steeps in alcohol, is placed under vacuum condition and keeps 1-180min；It then takes out and filters, the alcohol is methanol, ethyl alcohol, isopropyl
One of alcohol, n-butanol, n-hexyl alcohol or cyclohexanol.
7. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 2 certainly, which is characterized in that step
In rapid 4, calcining is specifically to be warming up to 400-1000 DEG C with the heating rate of 0.1-50 DEG C/min, keeps the temperature 0.5-24h.
8. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 2 certainly, which is characterized in that step
In rapid 5, the metal ion in metal ion solution is Sr2+、Ca2+、Ba2+、Co2+Or Mn2+One of, the concentration of metal ion
For 0.1-10000mM.
9. the method for preparing three-dimensional ordered macroporous titanate is sacrificed in original position according to claim 1 certainly, which is characterized in that step
In rapid 5, hydrothermal temperature is 80-250 DEG C, reaction time 0.1-100h.
10. a kind of three-dimensional ordered macroporous titanate, which is characterized in that use method system described in any one of claim 1-9
It is standby to obtain.
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