CN102631949A - Modified visible-light responsive titania doped photocatalyst and production method and uses thereof - Google Patents
Modified visible-light responsive titania doped photocatalyst and production method and uses thereof Download PDFInfo
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- CN102631949A CN102631949A CN2011100372320A CN201110037232A CN102631949A CN 102631949 A CN102631949 A CN 102631949A CN 2011100372320 A CN2011100372320 A CN 2011100372320A CN 201110037232 A CN201110037232 A CN 201110037232A CN 102631949 A CN102631949 A CN 102631949A
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- titanium dioxide
- trifluoroacetic acid
- visible light
- photochemical catalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 182
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 16
- 239000010865 sewage Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 104
- 239000003054 catalyst Substances 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- -1 polybutylene terephthalate Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 15
- 229940043267 rhodamine b Drugs 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 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 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 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
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a modified visible-light responsive titania doped photocatalyst and production method and uses thereof. The preparation method comprises the following steps that: titanate is hydrolyzed in a trifluoroacetic acid solution and dried to obtain a solid dry gel, and then the solid dry gel is re-dissolved in water, is added with a dopant, and is subjected to hydrothermal treatment to obtain the modified visible-light responsive titania doped photocatalyst. The titania photocatalyst obtained by the preparation method provided by the invention has good photocatalytic activity under irradiation of visible light and high photocatalytic activity. The preparation method is simple, and the equipment is easy to operate. The modified visible-light responsive titania doped photocatalyst can be directly used for photocatalytic degradation of organic pollutants in sewage treatment, and can be mixed with a polymer resin to be used as a composite photocatalyst.
Description
Technical field
The present invention relates to visible light-responsible titanium dioxide photochemical catalyst of doping vario-property and preparation method thereof; And the visible light-responsible titanium dioxide photochemical catalyst of this doping vario-property can directly be used for the organic pollution of photocatalytic degradation sewage, or with the purposes of mixed with polymers as composite photo-catalyst use aspect.
Background technology
Japanese scholar Fujishima found titanium dioxide (TiO since 1972
2) since the brine electrolysis, the light-catalyzed reaction technology has caused that as the potential approach that solves the energy and environmental problem people pay close attention to greatly.TiO
2Have the stable and advantages of environment protection of photocatalytic activity height, chemical property and think the catalysis material of tool development prospect.But, TiO
2Big (the energy gap E of Detitanium-ore-type of semiconductor light-catalyst energy gap broad, band-gap energy
g=3.2eV), can only the less ultraviolet light (wavelength is less than 400nm) of absorbing wavelength, and the light of inferior wave band less than 5% also in the sunshine gross energy, solar energy utilization ratio is low.On the other hand, nano-TiO
2Semiconductor light-catalyst light induced electron and hole are very easily compound, and photo-generated carrier efficient is low, and this has greatly limited its practical application.
In order to improve TiO
2The photoresponse scope of photochemical catalyst, the method that adopts at present mainly contain metal ion mixing and method such as nonmetallic ion-doped, for example Chinese invention patent CN1116927 disclose a kind of modified altogether solute doping prepare nano-TiO
2Method; Doped chemical is metals such as iron, copper; The photochemical catalyst particle mean size is 10～20nm, and the trap of interior focusing is 20～25% in the visible region, can utilize visible light sources such as sunshine or indoor incandescent lamp to realize photocatalysis; But the absorption of visible light rate is lower, can not make full use of solar energy.Another Chinese invention patent CN101791562 discloses the preparation method of a kind of iron, fluorin-doped nano-titanium dioxide visible light photocatalyst; But this method need just can obtain iron, fluorin-doped nano-titanium dioxide visible light photocatalyst through high-temperature calcination, and preparation cost is higher.
The titanium dioxide optical catalyst powder forms suspension system with treatment sewage in practical application, post-processed must be passed through methods such as filtrations, centrifugal, flocculation with its Separation and Recovery, and the process complicacy has increased recovery difficult, and cyclic utilization rate is low.Adopt polymer to recycle efficient for the preparing carriers composite photo-catalyst can improve greatly, easy to operate, for the visible light responsive photocatalyst of developing efficient stable provides new thinking.
Summary of the invention
The object of the present invention is to provide a kind of visible light-responsible titanium dioxide photochemical catalyst of doping vario-property.
Another object of the present invention is to provide that a kind of reaction condition is gentle, equipment needed thereby is simple, raw material is easy to get, be applicable to the preparation method of visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property of large-scale production.
A purpose more of the present invention is to provide a kind of purposes of visible light-responsible titanium dioxide photochemical catalyst of doping vario-property; The visible light-responsible titanium dioxide photochemical catalyst of this doping vario-property can directly be used for photocatalytic degradation sewage organic pollution, also can use as composite photo-catalyst with mixed with polymers.
The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property of the present invention is that drying obtains the solid, dry gel with titanate esters hydrolysis in trifluoroacetic acid solution, and is soluble in water again then, adds adulterant, carries out hydrothermal treatment consists and makes.The titanium dioxide optical catalyst that adopts preparation method of the present invention to obtain under radiation of visible light, has good photocatalytic activity and photocatalytic activity is high.Preparation method of the present invention is simple, the device therefor processing ease.The visible light-responsible titanium dioxide photochemical catalyst of this doping vario-property can directly be used for the photocatalytic degradation of sewage disposal organic pollution, also can mix as composite photo-catalyst with fluoropolymer resin and use.
The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property of the present invention; Be that finishing at titanium dioxide has trifluoroacetic acid and contains adulterant in titanium dioxide inside; Wherein the content of trifluoroacetic acid is 40～60wt%, and the content of adulterant is 0～5wt%, and surplus is a titanium dioxide.
Described adulterant is selected from FeCl
3, Fe (NO
3)
3, CuCl
2, Cu (NO
3)
2, Mn (CH
3COO)
2, AgNO
3, CH
3At least a in the group that COOAg etc. formed.
The preparation method of the visible light-responsible titanium dioxide photochemical catalyst of doping vario-property of the present invention may further comprise the steps:
(a) titanate esters is joined hydrolysis in the trifluoroacetic acid solution, wherein titanate esters: the mol ratio of trifluoroacetic acid is 1: 4～1: 10, and stirring at room (mixing time was generally 1～3 hour) obtains brown solution; Drying is also removed volatile accessory substance and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the water; Add adulterant; Carry out hydrothermal treatment consists (time of hydrothermal treatment consists was generally 3～10 hours) then, take out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains doping vario-property; Wherein the content of trifluoroacetic acid is 40～60wt%, and the content of adulterant is 0～5wt%, and surplus is a titanium dioxide.
Described titanate esters is selected from least a in the group that tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate form.
Described adulterant is selected from FeCl
3, Fe (NO
3)
3, CuCl
2, Cu (NO
3)
2, Mn (CH
3COO)
2, AgNO
3, CH
3At least a in the group that COOAg etc. formed.
The concentration of described trifluoroacetic acid solution is 50～99wt%.
The temperature of described hydrothermal treatment consists is 90～180 ℃.
The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property of the present invention can directly be used for the organic pollution of photocatalytic degradation sewage; Also can use as composite photo-catalyst with mixed with polymers; The organic pollution that is used for photocatalytic degradation sewage, wherein the content of polymer in composite photo-catalyst is 30～50wt%.
Described polymer is selected from least a in the group that polyvinyl alcohol, PETG, polybutylene terephthalate, Merlon, polycaprolactone, polymethyl methacrylate, polycaprolactam, polyvinyl acetate, PVP, polyacrylonitrile, polyacrylic acid etc. are formed.
The advantage of the visible light-responsible titanium dioxide photochemical catalyst of doping vario-property of the present invention is:
(1) preparation condition is gentle, and energy consumption is little, and cost is low, is suitable for large-scale production;
(2) have higher ultraviolet light and visible light catalysis activity simultaneously;
(3) composite photo-catalyst that obtains with mixed with polymers can repetitive cycling use, and is easy to operate.
Description of drawings
Fig. 1. the photoelectron spectroscopy of the visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property of the embodiment of the invention 1.
Fig. 2. the transmission electron microscope photo of the visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property of the embodiment of the invention 2.
The specific embodiment
Embodiment 1
(a) the 10ml tetraethyl titanate is joined in the trifluoroacetic acid solution that 9ml concentration is 99wt%, wherein tetraethyl titanate: the mol ratio of trifluoroacetic acid is 1: 4, and room temperature vigorous stirring 1 hour obtains brown solution; Drying is also removed volatile water byproduct, ethanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water; Place autoclave; 90 ℃ of hydrothermal treatment consists are after 10 hours; Take out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains having in the finishing of titanium dioxide the modification of trifluoroacetic acid, wherein the content of trifluoroacetic acid is 40wt%, and the content of titanium dioxide is 60wt%.The photoelectron of the visible light-responsible titanium dioxide photochemical catalyst of gained modification can be as shown in Figure 1.
Embodiment 2
(a) the 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 44.4ml concentration is 50wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 10, and room temperature vigorous stirring 3 hours obtains brown solution; Drying is also removed volatile water byproduct, butanols and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water; Place autoclave; 180 ℃ of hydrothermal treatment consists are after 3 hours; Take out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains having in the finishing of titanium dioxide the modification of trifluoroacetic acid, wherein the content of trifluoroacetic acid is 60wt%, and the content of titanium dioxide is 40wt%.The transmission electron microscope photo of the visible light-responsible titanium dioxide photochemical catalyst of gained modification is as shown in Figure 2.
Embodiment 3
(a) the 10ml tetraisopropyl titanate is joined in the trifluoroacetic acid solution that 16.7ml concentration is 80wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 6, and room temperature vigorous stirring 2 hours obtains brown solution; Drying is also removed volatile water byproduct, isopropyl alcohol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water; Place autoclave; 150 ℃ of hydrothermal treatment consists are after 5 hours; Take out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains having in the finishing of titanium dioxide the modification of trifluoroacetic acid, wherein the content of trifluoroacetic acid is 44wt%, and the content of titanium dioxide is 56wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the 0.2g modification that (c) step (b) is obtained joins in the rhodamine B aqueous solution that 50ml concentration is 30mg/L; Through solar radiation after 4 hours; The concentration of rhodamine B is reduced to 0.5mg/L, and the photocatalytic degradation rate of rhodamine B reaches 98.3%.
Embodiment 4
(a) mixture with 5ml tetraisopropyl titanate and 5ml tetra-n-butyl titanate joins in the trifluoroacetic acid solution that 10ml concentration is 99wt%; Tetra-n-butyl titanate wherein: tetraisopropyl titanate: the mol ratio of trifluoroacetic acid is 1: 1: 8; Room temperature vigorous stirring 2 hours obtains brown solution; Drying is also removed volatile water byproduct, isopropyl alcohol, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.05gFeCl
3Adulterant places autoclave, and 150 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing FeCl in titanium dioxide inside in the finishing of titanium dioxide after 3 hours
3The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property, wherein the content of trifluoroacetic acid is 40wt%, the content of adulterant is 5wt%, the content of titanium dioxide is 55wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the 0.2g doping vario-property that (c) step (b) is obtained joins in the rhodamine B aqueous solution that 50ml concentration is 30mg/L; Through solar radiation after 4 hours; The concentration of rhodamine B is reduced to 0.2mg/L, and the photocatalytic degradation rate of rhodamine B reaches 99.3%.
Embodiment 5
(a) the 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 22.2ml concentration is 50wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 5, and room temperature vigorous stirring 3 hours obtains brown solution; Drying is also removed volatile water byproduct, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.01g CuCl
2Adulterant places autoclave, and 150 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing CuCl in titanium dioxide inside in the finishing of titanium dioxide after 3 hours
2The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property, wherein the content of trifluoroacetic acid is 44wt%, the content of adulterant is 1wt%, the content of titanium dioxide is 55wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property that (c) 1g step (b) is obtained is distributed in the 20ml water; Getting the 0.8g polyvinyl alcohol is dissolved in the 30ml water; With the two mixing and stirring, obtain composite photo-catalyst after the drying, wherein the content of polymer is 44.4wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the rhodamine B aqueous solution that 50ml concentration is 30mg/L, and after 6 hours, the concentration of rhodamine B is reduced to 1.2mg/L through solar radiation, and the photocatalytic degradation rate of rhodamine B reaches 96%.
Embodiment 6
(a) the 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 11.2ml concentration is 99wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 5, and room temperature vigorous stirring 3 hours obtains brown solution; Drying is also removed volatile water byproduct, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.01g AgNO
3With 0.01g CH
3The COOAg adulterant places autoclave, and 150 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing AgNO in titanium dioxide inside in the finishing of titanium dioxide after 3 hours
3And CH
3The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property of COOAg, wherein the content of trifluoroacetic acid is 44wt%, and the content of adulterant is 2wt%, and the content of titanium dioxide is 54wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property that (c) 1g step (b) is obtained is distributed in the 20ml water; Getting the 0.6g PVP is dissolved in the 20ml water; With the two mixing and stirring, obtain composite photo-catalyst after the drying, wherein the content of polymer is 37.5wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the methyl orange aqueous solution that 50ml concentration is 30mg/L, and after 6 hours, the concentration of methyl orange is reduced to 0.6mg/L through solar radiation, and the photocatalytic degradation rate of methyl orange reaches 98%.
Embodiment 7
(a) mixture with 5ml tetraisopropyl titanate and 5ml tetra-n-butyl titanate joins in the trifluoroacetic acid solution that 10ml concentration is 99wt%; Tetra-n-butyl titanate wherein: tetraisopropyl titanate: the mol ratio of trifluoroacetic acid is 1: 1: 8; Room temperature vigorous stirring 2 hours obtains brown solution; Drying is also removed volatile water byproduct, isopropyl alcohol, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.01gFeCl
3And 0.01gCuCl
2Adulterant places autoclave, and 150 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing FeCl in titanium dioxide inside in the finishing of titanium dioxide after 3 hours
3And CuCl
2The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property, wherein the content of trifluoroacetic acid is 40wt%, the content of adulterant is 2wt%, the content of titanium dioxide is 58wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property that (c) 1g step (b) is obtained is distributed in the 20ml oxolane; Getting the 0.5g PETG is dissolved in the 20ml trifluoroacetic acid; Other gets the 0.5g polymethyl methacrylate and is dissolved in the 20ml oxolane; With three's mixing and stirring, obtain composite photo-catalyst after the drying, wherein the content of polymer is 50wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the aqueous solution of methylene blue that 50ml concentration is 30mg/L, and after 5 hours, the concentration of methylene blue is reduced to 0.8mg/L through solar radiation, and the photocatalytic degradation rate of methyl orange reaches 97.3%.
Embodiment 8
(a) the 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 14.8ml concentration is 90wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 6, and room temperature vigorous stirring 3 hours obtains brown solution; Drying is also removed volatile water byproduct, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.01gCuCl
2Adulterant places autoclave, and 150 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing CuCl in titanium dioxide inside in the finishing of titanium dioxide after 3 hours
2The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property, wherein the content of trifluoroacetic acid is 44wt%, the content of adulterant is 1wt%, the content of titanium dioxide is 55wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property that (c) 1g step (b) is obtained is distributed in the 20ml water; Getting the 0.43g polyvinyl alcohol is dissolved in the 30ml water; With the two mixing and stirring, obtain composite photo-catalyst after the drying, wherein the content of polymer is 30wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the rhodamine B aqueous solution that 50ml concentration is 30mg/L, and after 4 hours, the concentration of rhodamine B is reduced to 1.6mg/L through solar radiation, and the photocatalytic degradation rate of rhodamine B reaches 94.7%.
Embodiment 9
(a) the 10ml tetraethyl titanate is joined in the trifluoroacetic acid solution that 9ml concentration is 99wt%, wherein tetraethyl titanate: the mol ratio of trifluoroacetic acid is 1: 4, and room temperature vigorous stirring 1 hour obtains brown solution; Drying is also removed volatile water byproduct, ethanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water; Place autoclave; 180 ℃ of hydrothermal treatment consists are after 5 hours; Take out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains having in the finishing of titanium dioxide the modification of trifluoroacetic acid, wherein the content of trifluoroacetic acid is 40wt%, and the content of titanium dioxide is 60wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the modification that (c) 0.5g step (b) is obtained is distributed in the 20ml water; Getting the 0.5g polyvinyl alcohol is dissolved in the 30ml water; With the two mixing and stirring, obtain composite photo-catalyst after the drying, wherein the content of polymer is 50wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the rhodamine B aqueous solution that 50ml concentration is 30mg/L, and after 4 hours, the concentration of rhodamine B is reduced to 1.6mg/L through solar radiation, and the photocatalytic degradation rate of rhodamine B reaches 94.7%.
Embodiment 10
(a) the 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 13.8ml concentration is 80wt%, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1: 5, and room temperature vigorous stirring 3 hours obtains brown solution; Drying is also removed volatile water byproduct, n-butanol and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that 1g step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the 20ml water, adds 0.01g CuCl
2And 0.01gFeCl
3Adulterant places autoclave, and 180 ℃ of hydrothermal treatment consists were taken out drying and obtained trifluoroacetic acid being arranged and containing CuCl in titanium dioxide inside in the finishing of titanium dioxide after 5 hours
2And FeCl
3The visible light-responsible titanium dioxide photochemical catalyst of doping vario-property, wherein the content of trifluoroacetic acid is 43wt%, the content of adulterant is 2wt%, the content of titanium dioxide is 55wt%.
The visible light-responsible titanium dioxide photochemical catalyst of the doping vario-property that (c) 1g step (b) is obtained is distributed in the 20ml water; Getting 0.45g polyvinyl alcohol and 0.45g polyacrylic acid is dissolved in respectively in the 30ml water; With three's mixing and stirring; Obtain composite photo-catalyst after the drying, wherein the content of polymer is 47.4wt%.
(d) composite photo-catalyst that 0.2g step (c) is obtained joins in the methyl orange aqueous solution that 50ml concentration is 30mg/L, and after 4 hours, the concentration of methyl orange is reduced to 0.6mg/L through solar radiation, and the photocatalytic degradation rate reaches 98%.
Claims (10)
1. the visible light-responsible titanium dioxide photochemical catalyst of a doping vario-property; It is characterized in that: described photochemical catalyst is that the finishing at titanium dioxide has trifluoroacetic acid and contains adulterant in titanium dioxide inside; Wherein the content of trifluoroacetic acid is 40～60wt%; The content of adulterant is 0～5wt%, and surplus is a titanium dioxide.
2. the visible light-responsible titanium dioxide photochemical catalyst of doping vario-property according to claim 1, it is characterized in that: described adulterant is selected from FeCl
3, Fe (NO
3)
3, CuCl
2, Cu (NO
3)
2, Mn (CH
3COO)
2, AgNO
3, CH
3At least a in the group that COOAg formed.
3. the preparation method of the visible light-responsible titanium dioxide photochemical catalyst of a doping vario-property according to claim 1 and 2 is characterized in that, this method may further comprise the steps:
(a) titanate esters is joined hydrolysis in the trifluoroacetic acid solution, wherein titanate esters: the mol ratio of trifluoroacetic acid is 1: 4～1: 10, and stirring at room obtains brown solution; Drying is also removed volatile accessory substance and excessive trifluoroacetic acid, obtains the titanium dioxide xerogel that finishing has trifluoroacetic acid;
(b) finishing that step (a) is obtained has the titanium dioxide xerogel of trifluoroacetic acid to be dissolved in the water, and adds adulterant, carries out hydrothermal treatment consists then, takes out the dry visible light-responsible titanium dioxide photochemical catalyst that obtains doping vario-property; Wherein the content of trifluoroacetic acid is 40～60wt%, and the content of adulterant is 0～5wt%, and surplus is a titanium dioxide.
4. preparation method according to claim 3 is characterized in that: described titanate esters is selected from least a in the group that tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate form.
5. preparation method according to claim 3 is characterized in that: described adulterant is selected from FeCl
3, Fe (NO
3)
3, CuCl
2, Cu (NO
3)
2, Mn (CH
3COO)
2, AgNO
3, CH
3At least a in the group that COOAg formed.
6. preparation method according to claim 3 is characterized in that: the concentration of described trifluoroacetic acid solution is 50～99wt%.
7. preparation method according to claim 3 is characterized in that: the temperature of described hydrothermal treatment consists is 90～180 ℃.
8. according to claim 3 or 7 described preparation methods, it is characterized in that: the time of described hydrothermal treatment consists is 3～10 hours.
9. the purposes of the visible light-responsible titanium dioxide photochemical catalyst of a doping vario-property according to claim 1 and 2, it is characterized in that: the visible light-responsible titanium dioxide photochemical catalyst of described doping vario-property directly is used for the organic pollution of photocatalytic degradation sewage; Or the visible light-responsible titanium dioxide photochemical catalyst and the mixed with polymers of described doping vario-property use as composite photo-catalyst, is used for the organic pollution of photocatalytic degradation sewage, and wherein the content of polymer in composite photo-catalyst is 30～50wt%.
10. purposes according to claim 9 is characterized in that: described polymer is selected from least a in the group that polyvinyl alcohol, PETG, polybutylene terephthalate, Merlon, polycaprolactone, polymethyl methacrylate, polycaprolactam, polyvinyl acetate, PVP, polyacrylonitrile, polyacrylic acid form.
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| CN104588048A (en) * | 2015-01-14 | 2015-05-06 | 武汉理工大学 | Preparation method of efficient iron and fluorine double-auxiliary co-modified titanium dioxide photocatalytic material |
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