CN105921141A - Hierarchical porous strontium titanate microspheres and preparation and application thereof - Google Patents
Hierarchical porous strontium titanate microspheres and preparation and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 20
- 239000011543 agarose gel Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229920000936 Agarose Polymers 0.000 claims description 22
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 22
- 239000011806 microball Substances 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 18
- 239000000499 gel Substances 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 16
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 16
- 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 16
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910002367 SrTiO Inorganic materials 0.000 claims description 12
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- 235000011572 Pyrus ussuriensis Nutrition 0.000 description 4
- 244000173166 Pyrus ussuriensis Species 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 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 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Water Supply & Treatment (AREA)
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Abstract
The invention discloses hierarchical porous strontium titanate microspheres. An agarose gel template method and sol-gel method are employed to prepare SrTiO3 microspheres with porous structure; the SrTiO3 microspheres have particle size of 17-20 mum; the SrTiO3 microspheres are composed of a plurality of self-assembled cubic SrTiO3 monocrystal; the SrTiO3 microspheres are provided with primary pores and secondary pores; the primary pores have porosity of 70- 150 nm, and the secondary pores have diameter of 3nm. The strontium titanate microspheres obtained by the invention have high adsorption performance and catalytic performance, and the invention provides a novel method for the preparation of the macropore photocatalytic material. The strontium titanate microspheres show good photocatalytic reduction performance on chromium, and can be recovered by simple sedimentation method. The invention has the advantages of low price, easiness to obtain, simple preparation process, mild reaction conditions, greenness, and no secondary pollution.
Description
Technical field
The present invention relates to the preparation method of a kind of classifying porous strontium titanate visible light catalyst, belong to the synthesis field of inorganic functional material,
Can be applicable to remove the Cr VI in sewage.
Background technology
The industrial and mining establishment such as chemical industry, plating, leather the most all discharge substantial amounts of precious metal ion waste liquid, and hexavalent chromium is wherein
One of, if processing not in time, endangering environment, endangering human health.Photo catalytic reduction hexavalent chromium is that development in recent years rises
Come one be simple to operate and friendly to environment, high efficiency wastewater processing technology.Wherein ternary compound SrTiO3Have stable,
The advantage such as cheap.Hexavalent chromium is carried on strontium titanates surface, and under sufficiently strong illumination, quasiconductor strontium titanates is subject to
To exciting, there is electron transition, produce electronics and hole.A part of electronics and hole can move to the surface of catalyst with negative
Carry off son to react；A part of electronics and hole can be combined in quasiconductor, reduce catalytic efficiency.So suppression electronics and
The compound of hole becomes the important channel improving photocatalysis efficiency.
The approach of suppression electronics and hole-recombination mainly has at present: be combined with other semi-conducting material, with metal or nonmetal unit
Element doping, the regulation and control etc. of pattern.Wherein the one of porous material Morphological control, is widely studied, and is primarily due to porous
Structure is possible not only to reduce the compound of electronics and hole, and may be provided for more avtive spot, utilizes more illumination
Area, improves the catalytic performance of material,
The porous strontium titanate material prepared at present is mainly aperture and mesoporous, and the strontium titanate material of macropore does not the most grind
Study carefully.Emulsion template method is a kind of important channel preparing porous material in recent years.Emulsion particle can be at 10-1000nm yardstick
Change, and particle diameter and distribution adjustable controlled, thus can be used to prepare the porous material of more than mesopore and mesopore.
Summary of the invention
It is an object of the invention to provide a kind of method preparing porous strontium titanates catalysis material, this preparation method mild condition,
Preparation process is easy, controllability is good, graded porous structure, is applied to the research of reduction of hexavalent chromium, effect under simulated solar irradiation
Substantially.
In order to solve above-mentioned technical problem, a kind of classifying porous strontium titanates microsphere that the present invention proposes, is to utilize agarose to coagulate
What glue pattern plate method and sol-gal process were prepared has the SrTiO of loose structure3Microsphere, described SrTiO3The particle diameter of microsphere is
17 μm-20 μm, described SrTiO3Microsphere is by multiple Cubic SrTiO3Monocrystalline self assembly forms, described SrTiO3Microsphere is distributed
Having one-level hole and second hole gap, the aperture of described one-level hole is 70-150nm, and the aperture of second hole gap is 3nm.
Prepare above-mentioned classifying porous strontium titanates microsphere to comprise the following steps:
Step one, configuration contain agarose and the 6-18wt.%SrCO of 3wt.%3The aqueous solution of powder, ultrasonic 1h at 90 DEG C
Water bath with thermostatic control is heated, until agarose solution fully dissolves, for aqueous phase；Meanwhile, in the there-necked flask with agitator
Add 3.8wt.%Span 85, the cyclohexane solution of 1.6wt.%Tween 80, the water bath with thermostatic control of 60 DEG C stirred 5min,
Rotating speed is 1000r/min, for oil phase；Aqueous phase is 1:2 with the ratio of oil phase；
Step 2, it is 1:2 according to aqueous phase and oil phase ratio, pours rapidly the warmed-up aqueous phase in step one into oil phase, continue
60 DEG C of stirred in water bath 30min, rotating speed is 1000r/min；Then emulsion is transferred in the psychrolusia of 0 DEG C, protect
Hold identical rotating speed, stir 30min, low-temperature setting, be centrifuged, remove the oil phase on upper strata, with ethanol, deionized water repeatedly
Washing；Then filter successively with the standard screen of 200 mesh, 300 mesh, take the gel micro-ball between 200-300 mesh, and be saved in
In the ethanol solution of 20%, it is designated as SrCO3/ Agarose gel micro-ball.
Step 3, the SrCO that will obtain in step 23/ Agarose gel micro-ball 50% ethanol solution, 80% ethanol solution,
Soaking successively in 100% ethanol solution and 100% aqueous isopropanol, each soak time is 6h, the water in displacement gel micro-ball
Point；6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%；Afterwards with filter paper filtering, by gel micro-ball surface
Titanium isopropoxide solution blot；Subsequently, being immersed in the isopropanol water solution of 50%, soak 6h, hydrolysis mineralising obtains
SrCO3/Agarose/TiO2Microsphere；
Step 4, the SrCO that will obtain in step 33/Agarose/TiO2At 1000 DEG C, 10h is calcined after microsphere lyophilization；
The unreacted SrCO of removal is fully washed the most successively with dilute hydrochloric acid, deionized water3, at 60 DEG C, it is dried to obtain SrTiO3Micro-
Ball.
The classifying porous strontium titanates microsphere of the present invention, as photocatalyst, may be used for removing the Cr VI in sewage.
Compared with prior art, the invention has the beneficial effects as follows:
A kind of method that the present invention combines emulsion template with collosol and gel has been prepared containing macropore (i.e. one-level hole) and has been situated between
The SrTiO in hole (i.e. second hole gap)3Microsphere.Wherein, macropore is conducive to the refraction of light, increases the absorption area of light, mesoporous
Contribute to providing more avtive spot, therefore can improve absorption property and the catalytic performance of material.The present invention obtains
SrTiO3Microsphere is cube SrTiO being about 100nm by the length of side3Monocrystalline composition (as shown in Figure 4), except making full use of
Outside light, it is also possible to being combined of suppression electron-hole pair, improve photocatalysis efficiency.The SrTiO that the present invention is prepared3
Microsphere is for reducing the research of chromium, under conditions of pH=2, in 2h just can with 100% by hexavalent chrome reduction as trivalent chromium (as
Shown in Fig. 5).
The SrTiO that invention prepares3Microsphere has higher absorption property and catalytic performance, for other big aperture photocatalysis material
Preparation provide a new method.Strontium titanates microsphere shows the performance of good photo catalytic reduction chromium, can be by letter
Single sedimentation method just can reclaim.The present invention has cheap and easy to get, and preparation is simple, and reaction condition is gentle, green
Color, non-secondary pollution etc. has advantage.
Accompanying drawing explanation
Fig. 1 is the SrCO not calcined of embodiment 4 preparation3/Agarose/TiO2The optical microscope photograph of-18 microspheres；
Fig. 2 is scanning electron microscope (SEM) photo after the STO-18 catalyst calcination of embodiment 4 preparation；
Fig. 3 is mesoporous distribution (BET) curve after the STO-18 catalyst calcination of embodiment 4 preparation；
Fig. 4 is X-ray diffraction (XRD) curve after the STO-18 catalyst calcination of embodiment 4 preparation；
Fig. 5 be STO catalyst prepared by various embodiments of the present invention reduce under simulated solar irradiation Cr (VI) time hexavalent chromium concentration
Change over figure.
Detailed description of the invention
Being described in further detail technical solution of the present invention with specific embodiment below in conjunction with the accompanying drawings, described is embodied as
The present invention is only explained by example, not in order to limit the present invention.
Embodiment 1
Weigh 0.75g agarose, 1.5g strontium carbonate powder in the aqueous solution of 25mL.At 90 DEG C of thermostatted waters after ultrasonic 1h
Bath is heated, until agarose fully dissolves, for aqueous phase.Meanwhile, the there-necked flask with agitator adds 1.9g Span
85 (three oleic acid Pyrusussuriensis esters), 0.8g Tween 80 (Tween 80) and 50mL hexamethylene, stir in the water bath with thermostatic control of 60 DEG C
Mixing 5min, rotating speed is 1000r/min, for oil phase.Then aqueous phase is poured into rapidly oil phase, continues 60 DEG C of stirred in water bath
30min.Transfer to emulsion afterwards, in the psychrolusia of 0 DEG C, be stirred for 30min, after low-temperature setting with ethanol, go from
Sub-water cyclic washing.Obtain SrCO3/ Agarose-6 gel micro-ball.
By SrCO3/ Agarose gel micro-ball is 50%, in 80%, 100% ethanol solution and 100% aqueous isopropanol successively
Soaking, each soak time is 6h, 6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%.Use filter paper afterwards
Filter, blot the isopropyl titanate on surface.Subsequently, being immersed in the isopropanol water solution of 50%, soak 6h, hydrolysis mineralising obtains
To SrCO3/Agarose/TiO2-6 microspheres.Lyophilization, then calcines 10h at 1000 DEG C.Dilute hydrochloric acid, deionized water
Washing, obtain SrTiO after drying at 60 DEG C3Microsphere (represents with STO-6 in Fig. 5).
Embodiment 2
Weigh 0.75g agarose, 3g strontium carbonate powder in the aqueous solution of 25mL.90 DEG C of waters bath with thermostatic control after ultrasonic 1h
Middle heating, until agarose fully dissolves, for aqueous phase.Meanwhile, the there-necked flask with agitator adds 1.9g Span
85 (three oleic acid Pyrusussuriensis esters), 0.8g Tween 80 (Tween 80) and 50mL hexamethylene, stir in the water bath with thermostatic control of 60 DEG C
Mixing 5min, rotating speed is 1000r/min, for oil phase.Then aqueous phase is poured into rapidly oil phase, continues 60 DEG C of stirred in water bath
30min.Transfer to emulsion afterwards, in the psychrolusia of 0 DEG C, be stirred for 30min, after low-temperature setting with ethanol, go from
Sub-water cyclic washing.Obtain SrCO3/ Agarose-12 gel micro-ball.
By SrCO3/ Agaros-12 gel micro-ball, 50%, depends in 80%, 100% ethanol solution and 100% aqueous isopropanol
Secondary immersion, each soak time is 6h, 6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%.Afterwards with filter
Paper filters, and blots the isopropyl titanate on surface.Subsequently, it is immersed in the isopropanol water solution of 50%, soaks 6h, hydrolyze mineralising
Obtain SrCO3/Agarose/TiO2-12 microspheres.Lyophilization, then calcines 10h at 1000 DEG C.Dilute hydrochloric acid, deionization
Water washing, obtain SrTiO after drying at 60 DEG C3Microsphere (represents with STO-12 in Fig. 5).
Embodiment 3
Weigh 0.75g agarose, 3.75g strontium carbonate powder in the aqueous solution of 25mL.At 90 DEG C of constant temperature after ultrasonic 1h
Water-bath is heated, until agarose fully dissolves, for aqueous phase.Meanwhile, the there-necked flask with agitator adds 1.9g Span
85 (three oleic acid Pyrusussuriensis esters), 0.8g Tween 80 (Tween 80) and 50mL hexamethylene, stir in the water bath with thermostatic control of 60 DEG C
Mixing 5min, rotating speed is 1000r/min, for oil phase.Then aqueous phase is poured into rapidly oil phase, continues 60 DEG C of stirred in water bath
30min.Transfer to emulsion afterwards, in the psychrolusia of 0 DEG C, be stirred for 30min, after low-temperature setting with ethanol, go from
Sub-water cyclic washing.Obtain SrCO3/ Agarose-15 gel micro-ball.
By SrCO3/ Agarose-15 gel micro-ball is 50%, in 80%, 100% ethanol solution and 100% aqueous isopropanol
Soaking successively, each soak time is 6h, 6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%.Use afterwards
Filter paper filtering, blots the isopropyl titanate on surface.Subsequently, it is immersed in the isopropanol water solution of 50%, soaks 6h, hydrolyze ore deposit
Change and obtain SrCO3/Agarose/TiO2-15 microspheres.Lyophilization, then calcines 10h at 1000 DEG C.Dilute hydrochloric acid, go from
The washing of sub-water, obtain SrTiO after drying at 60 DEG C3Microsphere (represents with STO-15 in Fig. 5).
Embodiment 4
Weigh 0.75g agarose, 4.5g strontium carbonate powder in the aqueous solution of 25mL.At 90 DEG C of thermostatted waters after ultrasonic 1h
Bath is heated, until agarose fully dissolves, for aqueous phase.Meanwhile, the there-necked flask with agitator adds 1.9g Span
85 (three oleic acid Pyrusussuriensis esters), 0.8g Tween 80 (Tween 80) and 50mL hexamethylene, stir in the water bath with thermostatic control of 60 DEG C
Mixing 5min, rotating speed is 1000r/min, for oil phase.Then aqueous phase is poured into rapidly oil phase, continues 60 DEG C of stirred in water bath
30min.Transfer to emulsion afterwards, in the psychrolusia of 0 DEG C, be stirred for 30min, after low-temperature setting with ethanol, go from
Sub-water cyclic washing.Obtain SrCO3/ Agarose-18 gel micro-ball.
By SrCO3/ Agarose-18 gel micro-ball is 50%, in 80%, 100% ethanol solution and 100% aqueous isopropanol
Soaking successively, each soak time is 6h, 6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%.Use afterwards
Filter paper filtering, blots the isopropyl titanate on surface.Subsequently, it is immersed in the isopropanol water solution of 50%, soaks 6h, hydrolyze ore deposit
Change and obtain SrCO3/Agarose/TiO2-18 microspheres are (as shown in Figure 1, it can be seen that the distribution of gel micro-ball diameter is compared
Uniformly, size is between 75 microns-100 microns).Lyophilization, then calcines 10h at 1000 DEG C.Dilute hydrochloric acid, goes
Ionized water washing, obtain SrTiO after drying at 60 DEG C3Microsphere (represents with STO-18 in Fig. 5).
As in figure 2 it is shown, the catalyst surface of embodiment 4 preparation presents vermiform macroporous structure, size is 70-150nm；
As shown in Figure 3, it can be seen that also containing meso-hole structure in catalyst, hole size is about 3nm；As shown in Figure 4, it was demonstrated that SrTiO3
Existence, strontium titanate monocrystal presents cube shaped frame.
Comparative example 1
The method utilizing collosol and gel has prepared TiO2.Comprise the following steps that, titanium isopropoxide solution is progressively instilled volume ratio
For in the isopropanol water solution of 1:1, it is sufficiently stirred for 1h, centrifugal, at 800 DEG C, calcine 10h after drying, obtain Detitanium-ore-type
TiO2。
Comparative example 2
The TiO that will not calcine in comparative example 12With SrCO3Mix according to the ratio that mol ratio is 1:1, then exist
Calcine 10h at 1000 DEG C, obtain the SrTiO of not apertures3, Fig. 5 is designated as Pure STO.
Hexavalent chrome reduction is tested
The strontium titanates microsphere with the graded porous structure 20mg present invention prepared joins directly as catalyst
In the potassium bichromate solution of 20mL10mg/L, first lucifuge absorption 1h, take a sample.Then under the xenon lamp of 500W, often
1mL solution is taken every 0.5h.Using diphenylcarbazide (DPC) as developer.Ultraviolet-visible spectrophotometer (U-3010,
Hitachi) its light absorption value is detected at 540nm.
Test result indicate that, the Strontium carbonate contents of preparation is that the STO-12 catalyst of 12wt% is urged under conditions of simulated solar irradiation
Change efficiency the highest, just can be with 100% reduction of hexavalent chromium in 2h when pH=2, as shown in Figure 5.Close with the method using hydro-thermal
Become porous strontium titanate material (λ ＞ 365nm, in 2h, reduction effect reaches 90%) compared obvious advantage (Z.Zheng,
B.Huang,X.Qin,X.Zhang,Y.Dai,Facile synthesis of SrTiO3hollow microspheres built as
assembly of nanocubes and their associated photocatalytic activity,Journal of Colloid and
Interface Science,358(2011)68-72.+-).This good catalytic effect is due to by SrTiO3Crystal self assembly shape
The loose structure become, restrained effectively the compound of photo-generate electron-hole, improves photocatalytic activity, simultaneously macropore and mesoporous
Structure increase the absorption area of light, beneficially the carrying out of light-catalyzed reaction.
Although above in conjunction with accompanying drawing, invention has been described, but the invention is not limited in above-mentioned detailed description of the invention,
Above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is in the present invention
Enlightenment under, without deviating from the spirit of the invention, it is also possible to make many variations, these belong to the guarantor of the present invention
Within protecting.
Claims (3)
1. a classifying porous strontium titanates microsphere, it is characterised in that: it is to utilize agarose gel template and collosol and gel legal system
For the SrTiO with loose structure gone out3Microsphere, described SrTiO3The particle diameter of microsphere is 17 μm-20 μm, described SrTiO3
Microsphere is by multiple Cubic SrTiO3Monocrystalline self assembly forms, described SrTiO3Microsphere is distributed one-level hole and second hole gap,
The aperture of described one-level hole is 70-150nm, and the aperture of second hole gap is 3nm.
2. the preparation method of a classifying porous strontium titanates microsphere, it is characterised in that: comprise the following steps:
Step one, configuration contain agarose and the 6-18wt.%SrCO of 3wt.%3The aqueous solution of powder, ultrasonic 1h at 90 DEG C
Water bath with thermostatic control is heated, until agarose solution fully dissolves, for aqueous phase；Meanwhile, in the there-necked flask with agitator
Add 3.8wt.%Span 85, the cyclohexane solution of 1.6wt.%Tween 80, the water bath with thermostatic control of 60 DEG C stirred 5min,
Rotating speed is 1000r/min, for oil phase；Aqueous phase is 1:2 with the ratio of oil phase；
Step 2, it is 1:2 according to aqueous phase and oil phase ratio, pours rapidly the warmed-up aqueous phase in step one into oil phase, continue
60 DEG C of stirred in water bath 30min, rotating speed is 1000r/min；Then emulsion is transferred in the psychrolusia of 0 DEG C, protect
Hold identical rotating speed, stir 30min, low-temperature setting, be centrifuged, remove the oil phase on upper strata, with ethanol, deionized water repeatedly
Washing；Then filter successively with the standard screen of 200 mesh, 300 mesh, take the gel micro-ball between 200-300 mesh, and be saved in
In the ethanol solution of 20%, it is designated as SrCO3/ Agarose gel micro-ball.
Step 3, the SrCO that will obtain in step 23/ Agarose gel micro-ball 50% ethanol solution, 80% ethanol solution,
Soaking successively in 100% ethanol solution and 100% aqueous isopropanol, each soak time is 6h, the water in displacement gel micro-ball
Point；6h in the isopropanol water solution of the isopropyl titanate being then immersed in 50%；Afterwards with filter paper filtering, by gel micro-ball surface
Titanium isopropoxide solution blot；Subsequently, being immersed in the isopropanol water solution of 50%, soak 6h, hydrolysis mineralising obtains
SrCO3/Agarose/TiO2Microsphere；
Step 4, the SrCO that will obtain in step 33/Agarose/TiO2At 1000 DEG C, 10h is calcined after microsphere lyophilization；
The unreacted SrCO of removal is fully washed the most successively with dilute hydrochloric acid, deionized water3, at 60 DEG C, it is dried to obtain SrTiO3Micro-
Ball.
3. the application of a classifying porous strontium titanates microsphere, it is characterised in that: by by titanium classifying porous described in claim 2
The SrTiO that the preparation method of acid strontium microsphere prepares3Microsphere is as photocatalyst, for removing the Cr VI in sewage.
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