CN105944745A - TiO2 nanosphere as well as preparation method and application thereof - Google Patents
TiO2 nanosphere as well as preparation method and application thereof Download PDFInfo
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- CN105944745A CN105944745A CN201610319811.7A CN201610319811A CN105944745A CN 105944745 A CN105944745 A CN 105944745A CN 201610319811 A CN201610319811 A CN 201610319811A CN 105944745 A CN105944745 A CN 105944745A
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- titanium dioxide
- dioxide nanometer
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- crystal face
- nitrogen
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002077 nanosphere Substances 0.000 title abstract 11
- 239000013078 crystal Substances 0.000 claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
- 231100000719 pollutant Toxicity 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 86
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 68
- 239000004408 titanium dioxide Substances 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- 229940106691 bisphenol a Drugs 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000007146 photocatalysis Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- 229940011871 estrogen Drugs 0.000 claims description 5
- 239000000262 estrogen Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 4
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 15
- 238000013019 agitation Methods 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000825 ultraviolet detection Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 229910011210 Ti—O—N Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a TiO2 nanosphere as well as a preparation method and an application thereof. The nanosphere specifically refers to the TiO2 nanosphere co-modified with N and SnO and provided with an exposed (001) crystal face. The preparation method comprises the following steps: S1, preparing a TiO2 nanosphere provided with the exposed (001) crystal face; S2, preparing a TiO2 nanosphere modified with N and provided with the exposed (001) crystal face; S3, preparing the TiO2 nanosphere co-modified with N and SnO and provided with the exposed (001) crystal face. According to the TiO2 nanosphere co-modified with N and SnO and provided with the exposed (001) crystal face, reaction conditions are mild, the operation is simple, the preparation success rate is high, and the TiO2 nanosphere is easy to recover and reuse; besides, the band gap of TiO2 can be reduced, a heterojunction formed on the surface of the nanosphere can effectively increase the separation rate of photoelectron holes, accordingly, the modified TiO2 nanosphere has high photocatalytic activity under visible light and can be applied to photocatalytic degradation of wastewater pollutants.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of titanium dioxide nanometer microballoons and system thereof
Preparation Method and application.
Background technology
Photocatalysis technology is the wastewater processing technology that development in recent years is got up, under illumination effect, and Jing Guoyi
Serial reaction produces has the hydroxyl radical free radical of Strong oxdiative ability and super oxonium ion, and decomposition of degrading is organic
Polluter.In existing semiconductor light-catalyst, titanium dioxide has cheap, nontoxic without dirty because of it
The advantages such as dye, physical and chemical performance are stable, become one of most potential catalysis material.
TiO2The physical and chemical performance of crystal is not only relevant with particle diameter, surface area and pattern, and is had with it
Some high activity crystal faces are relevant, and wherein three dimensional structure exposes the TiO of [001] crystal face2Monocrystalline surface is long-pending more
Greatly, active site position more, its structure be possible to prevent nanometer sheet layer by layer between assemble, its degradating organic dye,
Pollutant performance is more preferable.But, the energy gap of titanium dioxide is wider, relatively low to the utilization rate of solar energy；
Light induced electron and the hole of titanium dioxide be easily combined, and these drawbacks limit titanium dioxide is as photocatalysis
The actual application of agent.
Therefore, the TiO that a kind of photocatalysis performance is excellent is prepared2Nano microsphere, is people in the art
The focus of member's research.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides one and prepare simply, mild condition,
It is prepared as power high, it is easy to reclaim and reuse, the band gap of titanium dioxide, surface shape can be shortened simultaneously
The hetero-junctions become can be effectively improved the separation rate of photo-generate electron-hole, significantly improves the dioxy of photocatalytic activity
Change titanium Nano microsphere and its preparation method and application.
A kind of titanium dioxide nanometer microballoons is provided one of for achieving the above object, present invention employs following skill
Art scheme:
A kind of titanium dioxide nanometer microballoons, for the titanium dioxide of co-modified exposure [001] crystal face of nitrogen and stannum oxide
Titanium Nano microsphere.
The preparation method of the two above-mentioned titanium dioxide nanometer microballoons of offer for achieving the above object, the present invention adopts
By techniques below scheme:
The preparation method of above-mentioned titanium dioxide nanometer microballoons, comprises the steps:
S1, the preparation of titanium dioxide nanometer microballoons of exposure [001] crystal face: the most successively with acetone, isopropanol,
Methanol ultrasonic degreasing titanium sheet, rinses with deionized water subsequently, dries under a nitrogen；Dried titanium sheet is put
Enter autoclave, add hydrofluoric acid solution, carry out hydro-thermal reaction；Autoclave is cooled to room temperature, gained titanium
Sheet is washed with deionized, and dries under nitrogen；Titanium sheet is positioned in Muffle furnace calcining；
The preparation of the titanium dioxide nanometer microballoons of exposure [001] crystal face that S2, nitrogen are modified: titanium sheet leaching is placed in
In ammonia, calcine in Muffle furnace afterwards, obtain the nano titania of exposure [001] crystal face that nitrogen is modified
Microsphere sample；
The preparation of the titanium dioxide nanometer microballoons of exposure [001] crystal face that S3, nitrogen and stannum oxide are co-modified: will
The titanium dioxide nanometer microballoons sample of exposure [001] crystal face that the described nitrogen that S2 prepares is modified is placed in autoclave
In, add containing SnCl4·5H2The alcohol mixed solution of O, carries out hydro-thermal reaction, prepares after washing and drying
Nitrogen and the titanium dioxide nanometer microballoons sample of co-modified exposure [001] crystal face of stannum oxide.
Preferably, in described step S1, in hydrofluoric acid solution, the volume fraction of Fluohydric acid. is 0.4～0.6%,
And hydrothermal temperature is 170～200 DEG C in step S1, the response time is 2～4h.
Preferably, in described step S1, after titanium sheet hydro-thermal reaction, the calcining heat in Muffle furnace is
450～600 DEG C, calcination time be 1～2h.
Preferably, titanium sheet is immersed in the ammonia of 1～2M 14～16h by described step S2.
Preferably, after in described step S2, titanium sheet ammonia soaks, the calcining heat in Muffle furnace is
400～500 DEG C, calcination time be 1～2h.
Preferably, SnCl in described step S34·5H2The concentration of O solution is 3～8mg/mL；And step
In S3, hydrothermal temperature is 150～180 DEG C, and the response time is 10～14h.
The three of the purpose of the present invention are to provide a kind of above-mentioned titanium dioxide nanometer microballoons and give up at photocatalytic degradation
Application on water pollutant.Wherein, Wastewater Pollutant includes organic dye, environmental estrogens and medicine.
Preferably, described organic dyestuff includes methyl orange and methylene blue；Environmental estrogens includes that many chlorine joins
Benzene class and bisphenol-A；Medicine includes quadracycline.
The beneficial effects of the present invention is:
1) nitrogen and the nano titania of co-modified exposure [001] crystal face of stannum oxide that, the present invention provides are micro-
Ball: at TiO2Doped with non-metals element in photocatalyst, can shorten band gap, by photoresponse scope from
Ultraviolet area of light is extended to the compound of visible domain, suppression light induced electron and hole, thus improves photocatalytic
Energy；It addition, the composite nano materials surface of semiconductor coupling forms hetero-junctions, photogenerated charge can be accelerated
Transfer, thus realize the separation in light induced electron and hole, improve photocatalysis performance.
2) nitrogen and the nano titania of co-modified exposure [001] crystal face of stannum oxide that, the present invention provides are micro-
The preparation method of ball is easy to operate, mild condition, and it is convenient to reclaim, reproducible.Concrete, the present invention
Preparation method synthesized by hydro-thermal method and infusion process, simple and easy to control, two step process modifies nitrogen and oxidation
Stannum to expose [001] crystal face titanium dioxide nanometer microballoons on, the shape of titanium dioxide nanometer microballoons will not be changed
Looks.
3), the present invention through the titanium dioxide nanometer microballoons of co-modified exposure [001] crystal face of nitrogen and stannum oxide,
There is narrower band gap width and higher visible absorption ability, effectively widen its suction at visible ray
Receipts scope, the heterojunction structure formed at stannum oxide and titanium dioxide surface reduces its light induced electron and hole
Recombination probability, improve its light conversion efficiency, at photocatalytic degradation environmental estrogens class thing such as bis-phenol
In the research of A, show the photocatalysis performance of excellence.
4), the photocatalyst that is prepared as substrate with titanium sheet of the present invention, compared to the titanium dioxide of powder,
Removal process is convenient, and its cyclic test simultaneously confirms the stability of its photocatalysis property.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the titanium dioxide nanometer microballoons exposing [001] crystal face in embodiment 1.
Fig. 2 is to block biconial decahedron in embodiment 2 to fail to be formed the SEM of the titanium dioxide of microsphere
Figure.
Fig. 3 is nitrogen and the titanium dioxide of co-modified exposure [001] crystal face of stannum oxide in embodiment 3
SEM schemes.
Fig. 4 is nitrogen and the titanium dioxide of co-modified exposure [001] crystal face of stannum oxide in embodiment 3
TEM schemes.
Fig. 5 is nitrogen and the titanium dioxide of co-modified exposure [001] crystal face of stannum oxide in embodiment 3
XRD figure.
Fig. 6 is the titanium dioxide of exposure [001] crystal face co-modified for nitrogen and stannum oxide in embodiment 3
XPS schemes.
Fig. 7 is the titanium dioxide of exposure [001] crystal face co-modified for nitrogen and stannum oxide in embodiment 3
EIS schemes.
Fig. 8 is that the titanium dioxide of nitrogen and co-modified exposure [001] crystal face of stannum oxide is to bisphenol-A absorption fall
Solution curve figure (ultraviolet light λ=365nm).
Fig. 9 is that the titanium dioxide of nitrogen and co-modified exposure [001] crystal face of stannum oxide is to bisphenol-A degraded weight
Utilize figure (ultraviolet light λ=365nm) again.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the present invention is carried out clear,
It is fully described by.Following example are only used for clearly illustrating technical scheme, and can not
Limit the scope of the invention with this.
Heretofore described method is conventional method if no special instructions.Described raw material is as without saying especially
Bright equal can obtain from open commercial sources.Following example all use and writes a Chinese character in simplified form: expose the two of [001] crystal face
TiOx nano microsphere is abbreviated as TiO2(001), the titanium dioxide of exposure [001] crystal face that nitrogen is modified is received
Meter Wei Qiu is abbreviated as N-TiO2(001), nitrogen and the titanium dioxide of co-modified exposure [001] crystal face of stannum oxide
Titanium Nano microsphere is abbreviated as SnO2/N-TiO2(001)。
Embodiment 1
Expose the preparation of the titanium dioxide nanometer microballoons of [001] crystal face
First titanium thin slice (50mm × 15mm, 0.25mm) is passed sequentially through acetone, isopropanol and methanol super
Sound defat, rinses with deionized water subsequently, puts in autoclave after drying under a nitrogen, add 60mL
Volume fraction is the hydrofluoric acid solution of 0.5%, and heated at constant temperature 3h at 180 DEG C is the coldest by autoclave
But to room temperature, gained sample is washed with deionized, and dries, be positioned in Muffle furnace, at 600 DEG C under nitrogen
Lower calcining 1.5h, obtains TiO2(001) photocatalyst.
As it is shown in figure 1, observe TiO with scanning electron microscope (SEM)2(001) pattern of catalyst.With
Above method gained exposes the titanium dioxide microballoon sphere size of [001] crystal face and is about 2 μm, and its exposed surface is limit
Long about 0.6 μm square [001] crystal face.
Embodiment 2:
Expose the preparation of the titanium dioxide nanometer microballoons of [001] crystal face
First titanium thin slice (50mm × 15mm, 0.5mm) is passed sequentially through acetone, isopropanol and methanol super
Sound defat, rinses with deionized water subsequently, puts in autoclave after drying under a nitrogen, add 60mL
Volume ratio is the hydrofluoric acid solution of 0.3%, heated at constant temperature 3h at 180 DEG C, by autoclave natural cooling
To room temperature, gained sample is washed with deionized, and dries, be positioned in Muffle furnace, at 600 DEG C under nitrogen
Lower calcining 1.5h, obtains TiO2Photocatalyst.
As in figure 2 it is shown, observe TiO with scanning electron microscope (SEM)2The pattern of catalyst, prepared TiO2
It is to block biconial decahedron, fails to be formed the TiO of micro-sphere structure2。
Embodiment 3
The preparation of the titanium dioxide nanometer microballoons of nitrogen and co-modified exposure [001] crystal face of stannum oxide
The TiO that will prepare in embodiment 12(001) 16h in the ammonia of 1M it is immersed in, in Muffle furnace
450 DEG C of calcining 1.5h, obtain N-TiO2(001), then by N-TiO2(001) proceed to autoclave, add
Enter 5mg/mL SnCl4·5H2The alcohol mixed solution of O, hydro-thermal reaction 12h at 150 DEG C, washing is dried
SnO is prepared after Gan2/N-TiO2(001)。
As it is shown on figure 3, observe SnO with scanning electron microscope (SEM)2/N-TiO2(001) shape of catalyst
Looks.The titanium dioxide microballoon sphere size co-modified with above method gained nitrogen and stannum oxide is about 2 μm, SnO2
Nano-particle is dispersed in N-TiO2(001) surface.
SnO is further looked at by transmission electron microscope2/N-TiO2(001) photocatalyst.By Fig. 4
Understanding, lattice fringe d found out by high resolution electron microscopy figure and electronogram200For 0.19nm, it is indicated that TiO2
Grow along [001] direction, SnO2(110) lattice fringe in face is 0.335nm, and SnO is described2Coupling
N-TiO2(001) hetero-junctions is formed.X-ray diffraction analyser (XRD) carries out crystal structure and divides
Analysis, as shown in Figure 5, diffraction maximum 2 θ value is 26.6 °, 33.9 ° with 51.8 ° difference corresponding SnO2(110),
(101), (211) crystal face, and its diffraction peak intensity is little, shows SnO2N-TiO is modified in success2(001)
On, and little even particulate dispersion.Component analysis is carried out with x-ray photoelectron spectroscopy (XPS), by
The full spectrogram of XPS of Fig. 6 understand, this complex is made up of Ti, O, F, N, Sn, and Ti mainly with
+ 4 valencys exist；F mainly exists with Ti-F form；N mainly exists with Ti-O-N form；Sn3d5/2's
In conjunction with being positioned at 486.4eV, Sn3d3/2Combination energy position 495.4eV, illustrate Sn mainly with+4 valencys exist.
SnO is characterized with electrochemical impedance (EIS)2/N-TiO2(001) electron transfer efficiency of composite,
As it is shown in fig. 7, with independent TiO2(001) contrast, SnO2/N-TiO2(001) electron transfer capacity
Strengthen.
Embodiment 4
The preparation method of the titanium dioxide nanometer microballoons of nitrogen and co-modified exposure [001] crystal face of stannum oxide
First titanium thin slice (50mm × 15mm, 0.25mm) is passed sequentially through acetone, isopropanol and methanol super
Sound defat, rinses with deionized water subsequently, puts in autoclave after drying under a nitrogen, add 60mL
Volume ratio is the hydrofluoric acid solution of 0.4%, heated at constant temperature 2h at 170 DEG C, by autoclave natural cooling
To room temperature, gained sample is washed with deionized, and dries, be positioned in Muffle furnace, at 450 DEG C under nitrogen
Lower calcining 1h, obtains TiO2(001) photocatalyst.
By TiO2(001) 16h in the ammonia of 1M it is immersed in, 400 DEG C of calcining 1h in Muffle furnace,
N-TiO2(001), then by N-TiO2(001) proceed to autoclave, add 3mg/mL SnCl4·5H2O
Alcohol mixed solution, hydro-thermal reaction 10h at 150 DEG C, after washing and drying prepare SnO2/N-TiO2
(001)。
Embodiment 5
The preparation method of the titanium dioxide nanometer microballoons of nitrogen and co-modified exposure [001] crystal face of stannum oxide
First titanium thin slice (50mm × 15mm, 0.25mm) is passed sequentially through acetone, isopropanol and methanol super
Sound defat, rinses with deionized water subsequently, puts in autoclave after drying under a nitrogen, add 60mL
Volume ratio is the hydrofluoric acid solution of 0.6%, heated at constant temperature 4h at 200 DEG C, by autoclave natural cooling
To room temperature, gained sample is washed with deionized, and dries, be positioned in Muffle furnace, at 600 DEG C under nitrogen
Lower calcining 2h, obtains TiO2(001) photocatalyst.
By TiO2(001) 14h in the ammonia of 2M it is immersed in, 500 DEG C of calcining 2h in Muffle furnace,
N-TiO2(001), then by N-TiO2(001) proceed to autoclave, add 10mg/mL SnCl4·5H2O
Alcohol mixed solution, hydro-thermal reaction 14h at 180 DEG C, after washing and drying prepare SnO2/N-TiO2
(001)。
Application examples 1
As a example by bisphenol-A, the SnO prepared by embodiment 32/N-TiO2(001) catalyst is in ultraviolet
The lower photocatalytic degradation of light irradiation:
The bisphenol-A solution 50mL taking 1M respectively is placed in 3 test tubes, is sequentially added into TiO2(001)、
N-TiO2And SnO (001)2/N-TiO2(001) titanium sheet.Light-catalyzed reaction instrument is tested,
Photocatalysis light source is (can arbitrarily to regulate light source height and wattage, λ=365nm) under 500W mercury lamp, mercury lamp
Cooled down by the condensed water in quartz double-jacket.When reacting initial, first by bisphenol-A aqueous solution secretly
Under state, magnetic agitation 30min is to guarantee that reactant reaches adsorption equilibrium at catalyst surface, takes about 0.5mL
Bisphenol-A solution measures concentration.Then illumination 60min, takes a sample, photocatalysis at interval of a period of time
Always with magnetic agitation in degradation process.Using hplc determination bisphenol A concentration, flowing is first mutually
Alcohol and water (V/V=7:3, flow velocity is 1mL/min).Bisphenol-A maximal ultraviolet detection absorbing wavelength is
278nm, calculates the clearance (C of bisphenol-A under the conditions of differential responses0-C)/C0。
As shown in Figure 8, after ultraviolet lighting 60min, TiO2(001)、N-TiO2(001) and
SnO2/N-TiO2(001) degradation rate of bisphenol-A is respectively 79.16%, 82.28%, 87.91%,
SnO is described2/N-TiO2(001) degradation property is substantially better than TiO2, and N-TiO (001)2(001),
As can be seen here, nitrogen is modified and can be shortened band gap, couples SnO2TiO2Nano material suppression light induced electron is empty
Cave is combined, and improves photocatalysis performance.
Application examples 2
As a example by bisphenol-A, the SnO prepared by embodiment 42/N-TiO2(001) catalyst is in ultraviolet
The lower photocatalytic degradation of light irradiation:
The bisphenol-A solution 50mL taking 1M respectively is placed in 3 test tubes, is sequentially added into TiO2(001)、
N-TiO2And SnO (001)2/N-TiO2(001) titanium sheet.Light-catalyzed reaction instrument is tested,
Photocatalysis light source is (can arbitrarily to regulate light source height and wattage, λ=365nm) under 500W mercury lamp, mercury lamp
Cooled down by the condensed water in quartz double-jacket.When reacting initial, first by bisphenol-A aqueous solution secretly
Under state, magnetic agitation 30min is to guarantee that reactant reaches adsorption equilibrium at catalyst surface, takes about 0.5mL
Bisphenol-A solution measures concentration.Then illumination 60min, takes a sample, photocatalysis at interval of a period of time
Always with magnetic agitation in degradation process.Using hplc determination bisphenol A concentration, flowing is first mutually
Alcohol and water (V/V=7:3, flow velocity is 1mL/min).Bisphenol-A maximal ultraviolet detection absorbing wavelength is
278nm, calculates the clearance (C of bisphenol-A under the conditions of differential responses0-C)/C0。
Application examples 3:
As a example by bisphenol-A, the SnO prepared by embodiment 52/N-TiO2(001) catalyst is in ultraviolet
The lower photocatalytic degradation of light irradiation:
The bisphenol-A solution 50mL taking 1M respectively is placed in 3 test tubes, is sequentially added into TiO2(001)、
N-TiO2And SnO (001)2/N-TiO2(001) titanium sheet.Light-catalyzed reaction instrument is tested,
Photocatalysis light source is (can arbitrarily to regulate light source height and wattage, λ=365nm) under 500W mercury lamp, mercury lamp
Cooled down by the condensed water in quartz double-jacket.When reacting initial, first by bisphenol-A aqueous solution secretly
Under state, magnetic agitation 30min is to guarantee that reactant reaches adsorption equilibrium at catalyst surface, takes about 0.5mL
Bisphenol-A solution measures concentration.Then illumination 60min, takes a sample, photocatalysis at interval of a period of time
Always with magnetic agitation in degradation process.Using hplc determination bisphenol A concentration, flowing is first mutually
Alcohol and water (V/V=7:3, flow velocity is 1mL/min).Bisphenol-A maximal ultraviolet detection absorbing wavelength is
278nm, calculates the clearance (C of bisphenol-A under the conditions of differential responses0-C)/C0。
Application examples 4
As a example by bisphenol-A, the SnO that recycling embodiment 3 prepares2/N-TiO2(001) catalyst
Photocatalytic degradation under ultraviolet light irradiates:
The bisphenol-A solution 50mL taking 1M respectively is placed in 3 test tubes, is sequentially added into TiO2(001)、
N-TiO2And SnO (001)2/N-TiO2(001) titanium sheet.Light-catalyzed reaction instrument is tested,
Photocatalysis light source is (can arbitrarily to regulate light source height and wattage, λ=365nm) under 500W mercury lamp, mercury lamp
Cooled down by the condensed water in quartz double-jacket.When reacting initial, first by bisphenol-A aqueous solution secretly
Under state, magnetic agitation 30min is to guarantee that reactant reaches adsorption equilibrium at catalyst surface, takes about 0.5mL
Bisphenol-A solution measures concentration.Then illumination 60min, takes a sample, photocatalysis at interval of a period of time
Always with magnetic agitation in degradation process.Using hplc determination bisphenol A concentration, flowing is first mutually
Alcohol and water (V/V=7:3, flow velocity is 1mL/min).Bisphenol-A maximal ultraviolet detection absorbing wavelength is
278nm, calculates the clearance (C of bisphenol-A under the conditions of differential responses0-C)/C0.Recycling every time
Experiment condition identical, use same SnO2/N-TiO2(001) catalyst, as each illumination 120mim
After end, rinse 6 times with deionized water, dry under a nitrogen, in order to use next time.
As shown in Figure 9, SnO is worked as2/N-TiO2(001), when catalyst reuses 3 times, it is to bis-phenol
The degradation efficiency of A the most significantly reduces.And owing to being grown directly upon in titanium sheet, very convenient recovery
Utilize, do not produce secondary pollution, thus, it can be known that SnO2/N-TiO2(001) catalyst be one very
The visible-light photocatalyst of effective and repeatable utilization, can be applicable in actual production.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement
And deformation, these improve and deformation also should be regarded as protection scope of the present invention.
Claims (10)
1. a titanium dioxide nanometer microballoons, it is characterised in that: for the exposure that nitrogen and stannum oxide are co-modified
[001] titanium dioxide nanometer microballoons of crystal face.
2. a preparation method for titanium dioxide nanometer microballoons as claimed in claim 1, its feature exists
In comprising the steps:
S1, the preparation of titanium dioxide nanometer microballoons of exposure [001] crystal face: the most successively with acetone, isopropanol,
Methanol ultrasonic degreasing titanium sheet, rinses with deionized water subsequently, dries under a nitrogen；Dried titanium sheet is put
Enter autoclave, add hydrofluoric acid solution, carry out hydro-thermal reaction；Autoclave is cooled to room temperature, gained titanium
Sheet is washed with deionized, and dries, titanium sheet is positioned in Muffle furnace calcining under nitrogen；
The preparation of the titanium dioxide nanometer microballoons of exposure [001] crystal face that S2, nitrogen are modified: titanium sheet leaching is placed in
In ammonia, calcine in Muffle furnace afterwards, obtain the nano titania of exposure [001] crystal face that nitrogen is modified
Microsphere sample；
The preparation of the titanium dioxide nanometer microballoons of exposure [001] crystal face that S3, nitrogen and stannum oxide are co-modified: will
The titanium dioxide nanometer microballoons sample of exposure [001] crystal face that the described nitrogen that S2 prepares is modified is placed in autoclave
In, add containing SnCl4·5H2The alcohol mixed solution of O, carries out hydro-thermal reaction, prepares after washing and drying
Nitrogen and the titanium dioxide nanometer microballoons sample of co-modified exposure [001] crystal face of stannum oxide.
The preparation method of a kind of titanium dioxide nanometer microballoons the most according to claim 2, its feature
It is: in described step S1, in hydrofluoric acid solution, the volume fraction of Fluohydric acid. is 0.4～0.6%, and step
In S1, hydrothermal temperature is 170～200 DEG C, and the response time is 2～4h.
4. according to the preparation method of a kind of titanium dioxide nanometer microballoons described in Claims 2 or 3, its
It is characterised by: in described step S1, after titanium sheet hydro-thermal reaction, the calcining heat in Muffle furnace is
450～600 DEG C, calcination time be 1～2h.
The preparation method of a kind of titanium dioxide nanometer microballoons the most according to claim 2, its feature
It is: titanium sheet is immersed in the ammonia of 1～2M 14～16h by described step S2.
6. according to the preparation method of a kind of titanium dioxide nanometer microballoons described in claim 2 or 5, its
It is characterised by: after in described step S2, titanium sheet ammonia soaks, the calcining heat in Muffle furnace is
400～500 DEG C, calcination time be 1～2h.
The preparation method of a kind of titanium dioxide nanometer microballoons the most according to claim 2, its feature
It is: SnCl in described step S34·5H2The concentration of O solution is 3～8mg/mL；And water in step S3
Thermal response temperature is 150～180 DEG C, and the response time is 10～14h.
8. a titanium dioxide nanometer microballoons as claimed in claim 1 pollutes at wastewater by photocatalysis
Application on thing.
The application of titanium dioxide nanometer microballoons the most according to claim 8, it is characterised in that: its
In, Wastewater Pollutant includes organic dye, environmental estrogens and medicine.
The application of titanium dioxide nanometer microballoons the most according to claim 9, it is characterised in that: institute
State organic dyestuff and include methyl orange and methylene blue；Environmental estrogens includes polychlorinated biphenyl and bisphenol-A；
Medicine includes quadracycline.
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