CN107963655A - Mixed phase mesoporous TiO 2, preparation method and the processing method that the organic pollution containing arsenic is removed using its photocatalysis - Google Patents
Mixed phase mesoporous TiO 2, preparation method and the processing method that the organic pollution containing arsenic is removed using its photocatalysis Download PDFInfo
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 116
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 36
- 238000003672 processing method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims description 22
- 230000008859 change Effects 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001927 high performance liquid chromatography-inductively coupled plasma mass spectrometry Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 230000037361 pathway Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 238000000802 evaporation-induced self-assembly Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229950002705 arsanilic acid Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 claims description 3
- 229960003052 roxarsone Drugs 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 4
- ZYMCGHKVJXMQRR-UHFFFAOYSA-N dimethylarsenic Chemical compound C[As]C ZYMCGHKVJXMQRR-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract 1
- 229940091658 arsenic Drugs 0.000 description 97
- HBNBMOGARBJBHS-UHFFFAOYSA-N dimethylarsane Chemical compound C[AsH]C HBNBMOGARBJBHS-UHFFFAOYSA-N 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000003651 drinking water Substances 0.000 description 6
- 235000020188 drinking water Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KRDDXSIKPQVLDP-UHFFFAOYSA-N methylarsenic Chemical compound [As]C KRDDXSIKPQVLDP-UHFFFAOYSA-N 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 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
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2006/16—Pore diameter
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses a kind of mixed phase mesoporous TiO 2, its preparation method and the processing method using its photocatalysis removal organic pollution containing arsenic.The mixed phase mesoporous TiO 2 is anatase and the mixed phase crystal form of rutile, has the hole of 3~25nm of particle diameter, and contains Lacking oxygen.The described method includes：1) template is dissolved in solvent, adds hydrochloric acid and sulfuric acid, stirring；2) titanate is added, stirring, occurs hydrolytic-polymeric reaction；3) drying is roasted after under protective atmosphere, obtains mixed phase mesoporous TiO 2；The mass ratio of hydrochloric acid, sulfuric acid and titanate is 140:46:300.The high efficiency photocatalysis degraded to low concentration DMA can be realized under visible light conditions using it, the removal rate of DMA is more than 95%, the present invention also have found optimal the mesoporous TiO 2 input amount and pH value of mixed phase mesoporous titanium dioxide photocatalytic degraded DMA, and disclose two catalytic degradation routes that DMA in water removal is removed in photocatalysis.
Description
Technical field
The invention belongs to water-treatment technology field, is related to a kind of mixed phase mesoporous TiO 2, preparation method and the usage, special
It is not related to a kind of mixed phase mesoporous TiO 2, its preparation method and organic pollution containing arsenic is removed using the optically catalytic TiO 2
Processing method.
Background technology
Drinking water is the important channel of arsenic exposure, it was reported that arsenic mainly exists in the form of inorganic arsenic in water, i.e. pentavalent
Arsenic As (V) and trivalent arsenic As (III).But the presence of the organic pollution containing arsenic can not be ignored, many cities are all on ground
Organo-arsenic is detected in table water and underground water, predominantly monomethyl arsenic (MMA) and dimethyl arsenic (dimethylarsine, DMA),
Its concentration range is 3.5 μ g/L to 233.9 μ g/L.The water quality detection of some areas is the results show that the content of dimethyl arsenic reaches always
20%, DMA of arsenic has carcinogenicity and genetoxic, can cause chromosome mutation, gene mutation and DNA missings.Therefore, go
Except the dimethyl arsenic in water body causes researcher's concern.
Many scientists have been directed to use iron, aluminium flocculating agent Adsorption organo-arsenic, but effect is bad, and find arsenic
Removal rate reduced with the increase of methyl content.Zhao et al. (R.Zhao, J.T.Novak, C.Douglas Goldsmith,
Waste Manage.33 (2013) 1207-1214.) result of study find, when doing flocculant arsenic removal with ferric trichloride, on an equal basis
Under the conditions of to the removal rate of As (V) than DMA high about 48%.Therefore, first pre-oxidation is carried out to it before Adsorption DMA to change into
As (V) is probably effective important means for removing DMA.But result of study shows, either traditional oxidant (such as permanganic acid
Potassium, sodium hypochlorite), or advanced oxidation agent (such as Fenton reagent and super oxygen), it all can not achieve the efficient oxidation degraded to DMA.
In addition, DMA usually has (ppb grades) with relatively low concentration in drinking water, the removal difficulty of DMA is more increased.
Research shows, using titanium dioxide photocatalyst, DMA the efficient oxidations first can be degraded into As (V), then pass through
Absorption As (V) realizes the final removal of arsenic, and approach is provided effectively to remove the DMA in drinking water.But due to titanium dioxide
It is low to solar energy trans-utilization rate, and photo-generate electron-hole is higher to recombination rate again, its photocatalytic activity is restricted.Therefore,
Researchers start to be directed to the photocatalytic activity for improving titanium dioxide, and main method includes：(1) forming hetero-junctions reduces dioxy
Change the band gap of titanium；(2) modified by defect and improve electron transfer rate；(3) density of increasing specific surface area increase avtive spot
Deng.In addition, the mechanism of optically catalytic TiO 2 degraded DMA is still not clear.Most researchers are thought in DMA photocatalytic degradation mistakes
It is mainly that hydroxyl radical free radical has played effect in journey.But NaKajima et al. is considered that hole and hydroxyl radical free radical play jointly
Effect (M.Tanaka, Y.Takahashi, N.Yamaguchi, Journal of Physics:Conference Series
430(2013)012100.)；Perhaps be then considered et al. hydroxyl radical free radical and super oxygen played jointly effect (Z.Xu, C.Jing,
F.Li,X.Meng,Environmental Science&Technology 42(2008)2349-2354.)。
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of mixed phase meso-porous titanium dioxide
Titanium, its preparation method and the processing method that organic pollution containing arsenic (such as dimethyl arsenic) is removed using its photocatalysis.The present invention
Using the photocatalytic activity for improving titanium dioxide as starting point, the mixed phase mesoporous TiO 2 with high catalytic activity is prepared for, is adopted
The DMA being completely removed with its photochemical catalytic oxidation in water, the present invention have further disclosed the machine that DMA in water removal is removed in photocatalysis
Reason, has also probed into the influence of pH and catalyst amounts to experiment.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of mixed phase mesoporous TiO 2, the mixed phase mesoporous TiO 2 is anatase
With the mixed phase crystal form of rutile, there is the hole of particle diameter 3nm~25nm, and contain Lacking oxygen.
In the mixed phase mesoporous TiO 2 of the present invention, the particle diameter in hole in 3nm~25nm, such as 3nm, 5nm, 7nm, 10nm,
12nm, 15nm, 20nm, 22nm, 24nm or 25nm etc..Preferably, the specific surface area of the mixed phase mesoporous TiO 2 exists
78.63cm2/ g~130.56cm2/ g, such as 80cm2/g、82cm2/g、85cm2/g、88cm2/g、90cm2/g、95cm2/g、
100cm2/g、105cm2/g、110cm2/g、120cm2/ g or 130cm2/ g etc..
Second aspect, the present invention provide the preparation method of mixed phase mesoporous TiO 2 as described in relation to the first aspect, the side
Method is evaporation induced self-assembly method, specifically includes following steps：
(1) template is dissolved in solvent, adds hydrochloric acid and sulfuric acid, stirring, obtains mixed liquor；
(2) titanate is added into mixed liquor, is stirred, hydrolytic-polymeric reaction occurs；
(3) it is transferred to after drying in reacting furnace, is roasted under protective atmosphere, obtain mixed phase mesoporous TiO 2；
Wherein, the mass ratio of hydrochloric acid, sulfuric acid and titanate is (100~160):(35~50):300, such as 100:50:
300、120:40:300、150:35:300、160:50:300 or 140:45:300 etc., it is preferably 140:46:300.
The method of the present invention is simple, and workable, cost is low and yield is big.Induced certainly by the evaporation of the solvent of the present invention
Construction from part, has been prepared oxygen-containing vacancy, has had the mixed phase mesoporous TiO 2 of high-specific surface area, improves the migration speed of electronics
Rate, reduces band gap, improves photocatalytic activity, use it for photochemical catalytic oxidation go water removal in monomethyl arsenic, dimethyl arsenic,
The organic pollution containing arsenic such as arsanilic acid and roxarsone, it is more excellent compared to commercial P25, effect.
As the optimal technical scheme of preparation method of the present invention, the template is polyethylene oxide-polycyclic oxygen third
Alkane-polyethylene oxide triblock copolymer, it is a kind of triblock copolymer, i.e. P123 templates.
Preferably, step (1) described solvent is ethanol.
Preferably, step (1) described hydrochloric acid is the concentrated hydrochloric acid that mass fraction is 36%-38%, mass fraction such as 36%,
36.5%th, 37%, 37.5% or 38% etc..
Preferably, the mass fraction of step (1) described sulfuric acid is 44%.
Preferably, the time of step (1) described stirring is 2h~5h, such as 2h, 2.5h, 3h, 4h or 5h etc., is preferably
3h。
In the present invention, step (1) stirring carries out at ambient temperature.
Preferably, step (2) described titanate is isopropyl titanate isopropyl titanate (TIPO).
Preferably, the time of step (2) described stirring is 18h~24h, such as 18h, 20h, 21h, 22h, 22.5h, 23h
Or 24h etc., it is preferably 20h.
Preferably, step (3) described drying is：It is first 2 days dry at 40 DEG C then 2 days dry at 100 DEG C.
Preferably, step (3) described protective atmosphere is nitrogen atmosphere.
Preferably, step (3) is described is roasted to：3h is first burnt at 650 DEG C, then 6h is burnt at 450 DEG C.
The third aspect, the present invention provides to remove using the mixed phase mesoporous titanium dioxide photocatalytic described in first aspect to be had containing arsenic
The processing method of organic pollutants, the treating method comprises：
The mixed phase mesoporous TiO 2 described in first aspect is added into the solution containing the organic pollution containing arsenic, in dark
Under the conditions of stirring and adsorbing, then solution is transferred in photo catalysis reactor, light-catalyzed reaction is carried out under illumination condition.
In the present invention, the organic pollution containing arsenic includes monomethyl arsenic, dimethyl arsenic, arsanilic acid and roxarsone etc.,
Preferably dimethyl arsenic (DMA).But the above-mentioned organic pollution containing arsenic enumerated is not limited to, other this areas are common to be had containing arsenic
Machine thing is also suitable the processing method of the present invention.
As the optimal technical scheme of processing method of the present invention, in the solution containing the organic pollution containing arsenic,
The concentration of the organic pollution containing arsenic is 100 μ g/L~1.4g/L, such as 100 μ g/L, 200 μ g/L, 400 μ g/L, 500 μ g/L, 650
μ g/L, 750 μ g/L, 850 μ g/L, 1000 μ g/L, 1.2g/L, 1.3g/L or 1.4g/L etc., are preferably the μ g/L of 100 μ g/L~500.
It is mostly in the prior art ppm grades for the concentration of organic pollution containing arsenic in the water body of processing, contains for lower
Arsenic organic pollution concentration is then difficult to efficiently remove, and the organic pollution containing arsenic (such as DMA) detected in actual drinking water
Concentration in the range of 50-300ppb, the prior art remove the organic pollution containing arsenic method there are significant limitations.
Mixed phase mesoporous titanium dioxide photocatalytic disclosed by the invention remove the processing method of the organic pollution containing arsenic relative to
The prior art has significant progress, it can not only remove the water of conventional ppm ranks organic pollution containing arsenic (such as DMA)
Body, can also handle that initial concentration is lower or even the water body of the organic pollution containing arsenic of 200ppb or so, concentration range are more sticked on
Actual water body concentration is bordering on, and the present invention can efficiently remove the reluctant low concentration of organic pollution containing arsenic water body, processing
The removal rate of the water body of concentration 100ppb~500ppb is more than 95%, to remove the low concentration organic contamination containing arsenic in drinking water
Thing provides effective ways, and the removal for the organic pollution containing arsenic in actual water body is more added with directive significance.
Preferably, the addition of the mixed phase mesoporous TiO 2 is 0.8g/L~1g/L, such as 0.8g/L, 0.85g/L,
0.88g/L, 0.9g/L, 0.95g/L or 1g/L etc..Under the experiment condition of this optimization, be conducive to obtain more preferably photocatalysis performance.
Preferably, the time of stirring and adsorbing is 0.5h~2h under the dark condition, for example, 0.5h, 0.6h, 0.7h,
0.8h, 1h, 1.2h, 1.5h or 2h etc., are preferably 1h.
During mesoporous titanium dioxide photocatalytic oxidation removal organic pollution containing arsenic, organic pollution containing arsenic is being situated between
The absorption on porous titanium dioxide surface is the committed step that reaction carries out.Therefore, in order to make photocatalysis remove organic pollution containing arsenic
Efficiency is optimal, we will first contain in an experiment arsenic organic pollutant solution under dark condition with a certain amount of mesoporous dioxy
Change titanium and 0.5h~2h (preferably 1h) is mixed, to realize adsorption equilibrium of the mesoporous TiO 2 to the organic pollution containing arsenic, so
Mixed liquor is positioned under illumination again afterwards and carries out light-catalyzed reaction.
Preferably, the illumination is irradiated for xenon lamp.
The light source used in existing photocatalytic degradation organic pollution containing arsenic experiment at present is all ultraviolet lamp, ultraviolet luminous energy
Amount is high, and common photochemical catalyst may be by ultraviolet light and realize photocatalysis.But the ultraviolet light in sunlight is seldom, only
Less than 5%, if photochemical catalyst can only utilize ultraviolet light to play photocatalysis, then the utilization rate to sunlight is very low
, there are significant limitations for the method for prior art removal organic pollution containing arsenic.
Mixed phase mesoporous titanium dioxide photocatalytic disclosed by the invention remove the processing method of the organic pollution containing arsenic relative to
The prior art has a significant progress, xenon lamp can simulated visible light, processing method of the invention not only is gone under ultraviolet light by photocatalysis
Except organic pollution containing arsenic, efficient light-catalyzed reaction removal can also be carried out under xenon lamp, visible ray or sunlight to be had containing arsenic
Organic pollutants, processing method of the invention can make full use of the visible ray that total radiation 50% is accounted in sunlight, and realization pair can
See efficiently using for light, improve the applicable light source range of photocatalysis organic pollution containing arsenic.
As the optimal technical scheme of processing method of the present invention, the processing method is further included containing organic containing arsenic
The step of pH value of the solution of pollutant and mixed phase mesoporous TiO 2 is adjusted to 3~10, such as adjust to 3,4,5,6,7,8,9
Or 10 etc., preferably adjust to 5~7.Under the experiment condition 5~7 of this optimization, be conducive to obtain more preferably photocatalysis performance.
Preferably, pH value is adjusted using any one in HCl or NaOH.
As the optimal technical scheme of processing method of the present invention, the processing method is additionally included in light-catalyzed reaction drop
During solving organic pollution containing arsenic, the concentration change of the arsenic of different shape is tested, so as to learn mixed phase mesoporous TiO 2
The conversion pathway of the organic pollution containing arsenic during photocatalytic degradation organic pollution containing arsenic.
" arsenic of different shape " of the present invention had both included the arsenic of different valence state, also including the methyl number with valence state connection not
Same arsenic (i.e. organo-arsenic, inorganic arsenic).
Preferably, the test is using High performance liquid chromatography-inductively coupled plasma mass spectrometry combination (High
Performance Liquid Chromatography–Inductively Coupled Plasma Mass
Spectrometry, HPLC-ICP-MS) method.
Preferably, the process of the test is：The water sample of 2ml is taken every 5min, and is filtered with 50 μm of filter membrane, mistake
Water sample after filter is measured with HPLC-ICP-MS methods, to determine that the arsenic concentration of different shape changes.
As the optimal technical scheme of processing method of the present invention, the processing method further includes：To containing having containing arsenic
Screening agent is added in the solution of organic pollutants and mixed phase mesoporous TiO 2, and by testing photocatalytic degradation organic contamination containing arsenic
The change of arsenic concentration during thing, to be which kind of active material contains degraded during definite mixed phase mesoporous titanium dioxide photocatalytic
Arsenic organic pollution has played effect.
It is which kind of active material has played work to degraded organic pollution containing arsenic to probe into this optimal technical scheme
With, in practical operation, it is necessary to set it is multigroup to form parallel laboratory test group, by the screening agent of not same-action (such as：Suppress hole
With the superoxide radical of absorption；Suppress superoxide radical；Suppress hydroxyl radical free radical；Suppress hole；Exclude dissolved oxygen) it is added to not
With in group, and a blank control group for being added without screening agent is reserved, other conditions are consistent.
Preferably, the screening agent includes sodium bicarbonate solution, 1,4-benzoquinone solution, t-butanol solution, triethanolamine and nitrogen
Gas.Sodium bicarbonate solution has the function that the superoxide radical for suppressing hole and absorption；1,4-benzoquinone solution, which has, suppresses super oxygen certainly
By the effect of base；T-butanol solution has the function that to suppress hydroxyl radical free radical；Triethanolamine has the function that to suppress hole；Nitrogen
It is passed through with certain flow velocity, the dissolved oxygen in solution can be excluded.
During the present invention is by organic pollution containing arsenic of degrading to mixed phase mesoporous titanium dioxide photocatalytic, active material closes
The research of keyness and the conversion pathway of organic pollution containing arsenic, it was found that mixed phase mesoporous titanium dioxide photocatalytic removes organic containing arsenic
The technical principle of pollutant, is specially：Mixed phase mesoporous TiO 2 produces light induced electron and hole, photoproduction electricity under light conditions
Son and hole can directly be reacted with the pollutant organic pollution containing arsenic on surface makes pollutant be degraded；Or light induced electron
With hole further with the oxygen in water or water reaction generation superoxide radical, hydroxyl radical free radical high activity species, these are given birth to
Into active specy again with the pollutant reaction in water, make pollutant obtain degraded remove.During light-catalysed, hole exists
The degraded of mixed phase mesoporous titanium dioxide photocatalytic plays conclusive effect during organic pollution containing arsenic, and superoxide radical is also sent out
The effect of having waved.
As the further preferred technical solution of processing method of the present invention, following steps are the treating method comprises：
The mixed phase meso-porous titanium dioxide described in claim 1 is added in DMA solution to concentration for the μ g/L of 100 μ g/L~500
Titanium, the addition for making mixed phase mesoporous TiO 2 are 0.8g/L~1g/L, then adjusted using HCl or NaOH the pH value of solution to
5~7, solution, is then transferred in photo catalysis reactor by stirring and adsorbing 1h under dark condition, and light is carried out under xenon lamp irradiation
Catalytic reaction degraded DMA and the concentration change for testing the arsenic of different shape in degradation process.
In this optimal technical scheme, under the xenon lamp irradiation of simulation natural light, mixed phase mesoporous TiO 2 exhibition of the invention
The performance of very excellent photocatalytic degradation low concentration DMA is revealed, its DMA removal rate is up to 98%, by testing degradation process
The concentration change of the arsenic of middle different shape, it was found that catalytic action mechanism includes two transduction pathway, and hole also plays
Facilitation.Two paths are respectively：1. DMA is first converted into MMA, further mineralising is As (V) to MMA；2. DMA is first converted into
MMA, MMA are reduced into As (III) again, and As (III) is last to be oxidized to As (V) again.Finally, the DMA in solution is with As's (V)
Form is by mesoporous TiO 2 Adsorption.
Compared with the prior art, the present invention has the advantages that：
1st, evaporation induced self-assembly method of the invention is simple, and workable, cost is low and yield is big.
2nd, mixed phase mesoporous TiO 2 of the invention is anatase and the mixed phase crystal form of rutile, which contains
There is Lacking oxygen, improve the migration rate of electronics, reduce band gap, improve photocatalytic activity；The ratio of the mesoporous TiO 2
Surface area is big, and exposed avtive spot is more, is conducive to the absorption to pollutant and photocatalytic degradation, and above-mentioned advantage is titanium dioxide
Application in photocatalysis provides guidance.
3rd, the mixed phase mesoporous TiO 2 of the present invention is used for photocatalysis and removes organic pollution containing arsenic, realized to containing arsenic
The efficient oxidation degraded of organic pollution, and realized by absorption degradation product and the final of the organic pollution containing arsenic in water is gone
Remove；
4th, the processing method of mixed phase mesoporous titanium dioxide photocatalytic removal organic pollution containing arsenic disclosed by the invention is opposite
There is significant progress in the prior art, it can not only remove the water body of conventional ppm ranks organic pollution containing arsenic, can be with
Handle that initial concentration is lower or even the water body of the organic pollution containing arsenic of 200ppb or so, concentration range are more close to actual water
Bulk concentration, and the present invention can efficiently remove the reluctant low concentration of organic pollution containing arsenic water body, concentration for the treatment of 100ppb
The removal rate of the water body of~500ppb has provided more than 95% to remove the low concentration organic pollution containing arsenic in drinking water
Efficacious prescriptions method, the removal for the organic pollution containing arsenic in actual water body is more added with directive significance.
5th, the processing method of mixed phase mesoporous titanium dioxide photocatalytic removal organic pollution containing arsenic disclosed by the invention is opposite
Have a significant progress in the prior art, xenon lamp can simulated visible light, processing method of the invention not only photocatalysis under ultraviolet light
Organic pollution containing arsenic is removed, efficient light-catalyzed reaction removal can also be carried out under xenon lamp, visible ray or sunlight and contains arsenic
Organic pollution, processing method of the invention can make full use of substantial amounts of visible ray in sunlight, and realizing has visible ray
Effect utilizes, and to the removal rate of the organic pollution containing arsenic more than 95%, improves the applicable light of photocatalysis organic pollution containing arsenic
Source range.
6th, added by varying mixed phase mesoporous titanium dioxide photocatalytic catalyst during organic pollution containing arsenic of degrading
The pH value of amount and solution, optimizes reaction condition.
7th, by adding different freedom during aoxidizing organic pollution containing arsenic in mixed phase mesoporous titanium dioxide photocatalytic
Base screening agent, it is which kind of free radical plays leading role during the reaction to illustrate, the results showed that, hole is in meso-porous titanium dioxide
Titanium photocatalytic degradation plays conclusive effect during organic pollution containing arsenic, superoxide radical has also played effect.
8th, the arsenic concentration change feelings of different shape during DMA are aoxidized by measuring mixed phase mesoporous titanium dioxide photocatalytic
Condition, illustrates the conversion pathway of mixed phase mesoporous titanium dioxide photocatalytic oxidation DMA, specifically, first, DMA is first converted into MMA,
Further mineralising is As (V) to MMA；Second, DMA is first converted into MMA, MMA is reduced into As (III) again, and As (III) is last again
It is oxidized to As (V).Finally, the DMA in solution in the form of As (V) by mesoporous TiO 2 Adsorption.
Brief description of the drawings
Fig. 1 be embodiment 1 mesoporous TiO 2 and comparative example 1 P25 XRD diffraction patterns.
Fig. 2 be embodiment 1 mesoporous TiO 2 and comparative example 1 P25 UV-Vis DRS result figure.
Fig. 3 be embodiment 1 mesoporous TiO 2 and comparative example 1 P25 ERS spectrograms.
Fig. 4 be embodiment 1 mesoporous TiO 2 and comparative example 1 P25 xps energy spectrum figure.
Fig. 5 is arsenic concentration versus time curve in embodiment 2.
Fig. 6 is in embodiment 4, when pH value is 3,4,5,6,7,8 and 9, arsenic removal rate and photocatalysis during adsorption equilibrium
At the end of arsenic removal rate result figure.
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A kind of mixed phase mesoporous TiO 2 is present embodiments provided, its preparation method is evaporation induced self-assembly method,
Step is：By the use of P123 as template, be dissolved in suitable ethanol, added in mixed liquor 1.4g concentrated hydrochloric acid and
The sulfuric acid of 0.46g, is stirred at room temperature 3h.Add 3g isopropyl titanate TIPO into mixed liquor, and stir 20h to ensure that TIPO fills
Divide hydrolytic polymerization.Then solution is separately dried two days in vacuum drying chamber in 40 DEG C and 100 DEG C of environment.The sample that will be obtained
It is placed in tube furnace and 3h is burnt in nitrogen atmosphere, then 450 DEG C of burning 6h in Muffle furnace, the sample finally obtained is mixed phase mesoporous two
Titanium oxide.
The characterization of mesoporous TiO 2：Pass through the mesoporous TiO 2 and the P25 materials of comparative example 1 obtained to the present embodiment 1
Material carries out a series of characterizations, discloses mesoporous TiO 2 and the design feature contrast of business P25.
The mesoporous TiO 2 crystal form and the P25 of comparative example 1 prepared by X-ray diffraction method (XRD) to the present embodiment 1 into
Characterization is gone, the result is shown in Figure 1, as seen from the figure, mesoporous TiO 2 prepared by the present embodiment 1 are the mixed of anatase and Rutile Type
Synthetic type.
Further the mesoporous TiO 2 pattern of preparation is characterized by transmission electron microscope (TEM), by measuring material
The spacing of lattice of material further demonstrates the mixing crystal form that material is anatase and Rutile Type.
The mesoporous TiO 2 that is prepared by UV-Vis DRS (UV-Vis) to the present embodiment 1 and comparative example 1
The light abstraction width of P25 is characterized, and the result is shown in Fig. 2, and as seen from the figure, the light abstraction width generation of mesoporous TiO 2 is red
Move, the P25 of business is higher than to the absorption rate of light.
By the free resonance spectrum of electronics (ESR) and x-ray photoelectron spectroscopy (XPS) further to Jie of the present embodiment 1
The microscopic appearance of porous titanium dioxide and the P25 of comparative example 1 are characterized, and as a result see Fig. 3 and Fig. 4 respectively, can by Fig. 3 and Fig. 4
Know, Lacking oxygen is contained in mesoporous TiO 2, and substantial amounts of free radical activity material can be produced under light illumination.
In summary, the mesoporous TiO 2 of preparation is mixed phase, contains Lacking oxygen, and its specific surface area is higher than P25, because
This, the photocatalysis performance of mesoporous TiO 2 is better than P25.
Embodiment 2
It is to add appropriate meso-porous titanium dioxide in the DMA solution of 200 μ g/L to the initial concentration of 100ml in experimentation
Titanium, solution is first placed on magnetic stirring apparatus, 1h is adsorbed under dark condition, solution then is transferred to photo catalysis reactor again
In, carry out light-catalyzed reaction under xenon lamp irradiation.Under same experiment condition, mesoporous TiO 2 is changed to same dosage
Commercial P25, carry out contrast experiment.By measuring total arsenic concentration in reaction process in solution, contrast mesoporous TiO 2 and
The effect of P25 photocatalytic degradations DMA.Arsenic concentration versus time curve is shown in Fig. 5, the results showed that, under similarity condition, mesoporous two
Titanium oxide to the P25 high about 43% of the adsorbance of DMA than comparative example 1, mesoporous TiO 2 to the photocatalysis efficiency of DMA also above
P25。
Embodiment 3
It is to add different amounts of mesoporous two in the DMA solution of 200 μ g/L to the initial concentration of 100ml in experimentation
Titanium oxide, solution is first placed on magnetic stirring apparatus, 1h is adsorbed under dark condition, and it is anti-that solution then is transferred to photocatalysis again
Answer in device, light-catalyzed reaction is carried out under xenon lamp irradiation.By measuring under different mesoporous TiO 2 dosages, photocatalytic degradation
The change of arsenic concentration during DMA, determines the optimum dosage of mesoporous TiO 2.The result shows that when mesoporous TiO 2
When dosage is 0.8g/L-1g/L, photocatalysis effect is optimal.
Embodiment 4
It is to add a certain amount of mesoporous two in the DMA solution of 200 μ g/L to the initial concentration of 100ml in experimentation
Titanium oxide, 3-10 is adjusted to certain density NaOH and HCl respectively by the pH of solution.The solution of different pH is first placed in magnetic force to stir
Mix on device, 1h is adsorbed under dark condition, then solution is transferred in photo catalysis reactor again, light is carried out under xenon lamp irradiation
Catalytic reaction.By measuring under condition of different pH, the change of arsenic concentration (can be flat by adsorbing during photocatalytic degradation DMA
The arsenic removal rate at the end of arsenic removal rate and photocatalysis during weighing apparatus embodies), determine mesoporous titanium dioxide photocatalytic oxidation DMA's
Optimum PH range.The result shows that when pH is 5~7, photocatalysis effect is best.
In the present embodiment 4, when pH value is 3,4,5,6,7,8 and 9, arsenic removal rate and photocatalysis during adsorption equilibrium terminate
When arsenic removal rate result figure referring to Fig. 6, as seen from the figure, when pH is 5~7, photocatalysis effect is best.
Embodiment 5
It is to add appropriate meso-porous titanium dioxide in the DMA solution of 1.4g/L to the initial concentration of 100ml in experimentation
Titanium, solution is first placed on magnetic stirring apparatus, 1h is adsorbed under dark condition, solution then is transferred to photo catalysis reactor again
In, carry out light-catalyzed reaction under xenon lamp irradiation.The arsenic concentration of different shape in reaction process is measured by using HPLC-ICP-MS
Change, can learn the conversion pathway of DMA during mesoporous titanium dioxide photocatalytic degraded DMA.The result shows that meso-porous titanium dioxide
During titanium photocatalytic degradation DMA, the conversion pathway of DMA mainly includes two：First, DMA is first converted into MMA, MMA is again into one
Step mineralising is As (V)；Second, DMA elder generations DMA is first converted into MMA, MMA is reduced into As (III) again, and As (III) is last again by oxygen
Turn to As (V).Finally, the DMA in solution in the form of As (V) by mesoporous TiO 2 Adsorption.
Embodiment 6
In experimentation, it is assembled with to 6 in the DMA solution that 100ml initial concentrations are 200 μ g/L and adds phase homogeneity respectively
The mesoporous TiO 2 of amount.6 groups of mixed liquors are first respectively placed on magnetic stirring apparatus, 1h is adsorbed under dark condition.Then will
Solution is transferred in photo catalysis reactor, is added excessive sodium bicarbonate solution into 5 groups of solution respectively and (is suppressed hole and absorption
Superoxide radical), 1,4-benzoquinone solution (suppression superoxide radical), t-butanol solution (suppression hydroxyl radical free radical), triethanolamine
The nitrogen of (suppression hole) and certain flow rate (excluding the dissolved oxygen in solution) is used as screening agent, and remaining one group is used as blank pair
According to.Light-catalyzed reaction is carried out next, 6 groups of solution are placed under xenon lamp.6 groups of solution that different screening agents are added by measuring exist
The change of arsenic concentration during photocatalytic degradation DMA, determines which kind of active matter during mesoporous titanium dioxide photocatalytic degraded DMA
Kind has played effect.
The result shows that hole plays conclusive effect during mesoporous titanium dioxide photocatalytic degrades DMA, super oxygen is certainly
Effect has also been played by base.
Comparative example 1
The sample of this comparative example is commercial P25.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of mixed phase mesoporous TiO 2, it is characterised in that the mixed phase mesoporous TiO 2 is anatase and rutile
Mixed phase crystal form, has the hole of particle diameter 3nm~25nm, and contains Lacking oxygen.
2. mixed phase mesoporous TiO 2 according to claim 1, it is characterised in that the ratio of the mixed phase mesoporous TiO 2
Surface area is in 78.63cm2/ g~130.56cm2/g。
3. the preparation method of mixed phase mesoporous TiO 2 as claimed in claim 1 or 2, it is characterised in that the method is molten
Agent evaporation-induced self-assembly method, specifically includes following steps：
(1) template is dissolved in solvent, adds hydrochloric acid and sulfuric acid, stirring, obtains mixed liquor；
(2) titanate is added into mixed liquor, is stirred, hydrolytic-polymeric reaction occurs；
(3) it is transferred to after drying in reacting furnace, is roasted under protective atmosphere, obtain mixed phase mesoporous TiO 2；
Wherein, the mass ratio of hydrochloric acid, sulfuric acid and titanate is (100~160):(35~50):300, it is preferably 140:46:300.
4. according to the method described in claim 3, it is characterized in that, step (1) described template is polyethylene oxide-polycyclic oxygen
Propane-polyethylene oxide triblock copolymer, i.e. P123 templates；
Preferably, step (1) described solvent is ethanol；
Preferably, step (1) described hydrochloric acid is the concentrated hydrochloric acid that mass fraction is 36%~38%；
Preferably, the mass fraction of step (1) described sulfuric acid is 44%；
Preferably, the time of step (1) described stirring is 2h~5h, is preferably 3h；
Preferably, step (2) described titanate is isopropyl titanate isopropyl titanate；
Preferably, the time of step (2) described stirring is 18h~24h, is preferably 20h；
Preferably, step (3) described drying is：It is first 2 days dry at 40 DEG C then 2 days dry at 100 DEG C；
Preferably, step (3) described drying carries out in vacuum drying chamber；
Preferably, step (3) described protective atmosphere is nitrogen atmosphere；
Preferably, step (3) is described is roasted to：3h is first burnt at 650 DEG C, then 6h is burnt at 450 DEG C.
5. a kind of mixed phase mesoporous titanium dioxide photocatalytic using described in claim 1 removes the processing side of the organic pollution containing arsenic
Method, it is characterised in that the treating method comprises：
The mixed phase mesoporous TiO 2 described in claim 1 is added into the solution containing the organic pollution containing arsenic, in dark bar
Solution, is then transferred in photo catalysis reactor by stirring and adsorbing under part, and light-catalyzed reaction is carried out under illumination condition.
6. processing method according to claim 5, it is characterised in that the organic pollution containing arsenic includes：Monomethyl arsenic
In MMA, dimethyl arsenic DMA, arsanilic acid or roxarsone any one or at least two combination, be preferably DMA；
Preferably, in the solution containing the organic pollution containing arsenic, the concentration of the organic pollution containing arsenic for 100 μ g/L~
1.4g/L, is preferably the μ g/L of 100 μ g/L~500；
Preferably, the addition of the mixed phase mesoporous TiO 2 is 0.8g/L~1g/L；
Preferably, the time of stirring and adsorbing is 0.5h~2h under the dark condition, is preferably 1h；
Preferably, the illumination is irradiated for xenon lamp.
7. the processing method according to claim 5 or 6, it is characterised in that the processing method is further included containing containing arsenic
The step of pH value of the solution of organic pollution and mixed phase mesoporous TiO 2 is adjusted to 3~10, preferably adjust most 5~7；
Preferably, pH value is adjusted using any one in HCl or NaOH.
8. according to claim 5-7 any one of them processing methods, it is characterised in that the processing method further includes：In light
During catalytic reaction degraded organic pollution containing arsenic, the concentration change of the arsenic of different shape is tested, so as to learn that mixed phase is situated between
The conversion pathway of the organic pollution containing arsenic during porous titanium dioxide photocatalytic degradation organic pollution containing arsenic；
Preferably, the test is using High performance liquid chromatography-inductively coupled plasma mass spectrometry combination HPLC-ICP-MS methods；
Preferably, the process of the test is：The water sample of 2ml is taken every 5min, and is filtered with 50 μm of filter membrane, after filtering
Water sample with HPLC-ICP-MS methods measure, with determine different shape arsenic concentration change.
9. according to claim 5-8 any one of them processing methods, it is characterised in that the processing method further includes：Xiang Han
Have and screening agent is added in the solution of organic pollution containing arsenic and mixed phase mesoporous TiO 2, and contain arsenic by testing photocatalytic degradation
The change of arsenic concentration during organic pollution, to determine the mixed phase mesoporous titanium dioxide photocatalytic degraded mistake of organic pollution containing arsenic
Which kind of active material has played effect in journey；
Preferably, the screening agent includes sodium bicarbonate solution, 1,4-benzoquinone solution, t-butanol solution, triethanolamine and nitrogen.
10. such as claim 5-9 any one of them processing methods, it is characterised in that the treating method comprises following steps：
The mixed phase mesoporous TiO 2 described in claim 1 is added in DMA solution to concentration for the μ g/L of 100 μ g/L~500, is made
The addition of mixed phase mesoporous TiO 2 is 0.8g/L~1g/L, and the pH value of solution is then adjusted using HCl or NaOH to 5~7,
Solution, is then transferred in photo catalysis reactor by stirring and adsorbing 1h under dark condition, and photocatalysis is carried out under xenon lamp irradiation
Reaction degraded DMA and the concentration change for testing the arsenic of different shape in degradation process.
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| CN110143611A (en) * | 2019-05-07 | 2019-08-20 | 武汉理工大学 | Anatase/rutile compound phase TiO2The liquid phase preparation process of photocatalysis and energy storage material |
| CN110143611B (en) * | 2019-05-07 | 2020-10-30 | 武汉理工大学 | Anatase/rutile composite phase TiO2Liquid phase preparation method of photocatalysis and energy storage material |
| CN110302771A (en) * | 2019-06-26 | 2019-10-08 | 浙江工业大学 | Utilize the method for Organic- arsenic pollution in order mesoporous layered double hydroxide control water |
| CN110681380A (en) * | 2019-10-22 | 2020-01-14 | 吉林师范大学 | Preparation of high-efficiency hydrogen production catalyst Au-HSTiO by liquid phase reduction2Method (2) |
| CN110776079A (en) * | 2019-11-07 | 2020-02-11 | 合肥工业大学 | Method for promoting phenol pollutants to be efficiently photo-catalytically oxidized in situ by utilizing organic arsenic pollutants |
| CN110776079B (en) * | 2019-11-07 | 2022-03-15 | 合肥工业大学 | Method for promoting phenol pollutants to be efficiently photo-catalytically oxidized in situ by utilizing organic arsenic pollutants |
| CN113198302A (en) * | 2021-04-15 | 2021-08-03 | 成都安捷芮环保科技有限公司 | SRR free radical cluster medicament for treating various VOCs (volatile organic compounds) foul waste gas |
| CN113457719A (en) * | 2021-06-30 | 2021-10-01 | 中国人民解放军火箭军工程大学 | Titanium dioxide/SBA-15 compound, preparation method and application thereof, and treatment method of hydrazine organic matter |
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