CN108579737A - A kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst - Google Patents
A kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst Download PDFInfo
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- CN108579737A CN108579737A CN201810089025.1A CN201810089025A CN108579737A CN 108579737 A CN108579737 A CN 108579737A CN 201810089025 A CN201810089025 A CN 201810089025A CN 108579737 A CN108579737 A CN 108579737A
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 61
- 239000004408 titanium dioxide Substances 0.000 title claims description 8
- 239000002101 nanobubble Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 23
- 239000000413 hydrolysate Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 150000003608 titanium Chemical class 0.000 claims abstract description 17
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 74
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 229910010298 TiOSO4 Inorganic materials 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 34
- 238000006731 degradation reaction Methods 0.000 abstract description 34
- 239000010931 gold Substances 0.000 abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 231100000331 toxic Toxicity 0.000 abstract description 7
- 230000002588 toxic effect Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 5
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 62
- 239000002105 nanoparticle Substances 0.000 description 21
- 238000012545 processing Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000969 carrier Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- -1 hydroxyl radical free radical Chemical class 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
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- 238000007689 inspection Methods 0.000 description 3
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- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- QKUASTPMULFGLE-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4].[Au+3] Chemical compound [C+4].[O-2].[O-2].[Ti+4].[Au+3] QKUASTPMULFGLE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical class CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of the titanium dioxide carbon nanotube composite photo-catalyst of decorated by nano-gold, include the following steps：Using the aqueous solution of alcohol and steady-state gas as medium, is handled using micro-nano bubble generator, obtain micro-nano bubble water；The micro-nano bubble water, carbon nanotube and titanium salt are mixed and disperseed, dispersion liquid is obtained；The dispersion liquid is mixed with ammonia spirit, is hydrolyzed, hydrolysate is obtained；D) after mixing the hydrolysate with gold salt, micro-nano bubble water, photoreduction is carried out successively and heating is reacted, obtains reaction product；The reaction product is heat-treated, Au TiO are obtained2CNTs composite photo-catalysts.Provided by the invention preparation method is simple, enormously simplifies preparation process；And composite photo-catalyst obtained combines and stablizes, and has effective and excellent catalytic degradation effect；Meanwhile preparation process significantly reduces cost and the harm to environment without using toxic organic solvent and template.
Description
Technical field
The invention belongs to technical field of air purification, more particularly to titanium dioxide-carbon nanotube of a kind of decorated by nano-gold
The preparation method of composite photo-catalyst.
Background technology
Currently, with Typical Volatile Organic (VOCs) in the air pollutants of representative, many substances have carcinogenic cause
Abnormal effect will produce a series of chronic diseases after human body Long Term Contact.Therefore, the effective management and control and elimination of typical VOCs are become
One of hot spot studied at present especially researches and develops air purifying process that is lasting, efficient, stablizing, for energy-saving and emission-reduction, reduces poison
The generation of evil particulate matter, bettering people's living environment conscientiously is of great significance.
Wherein, photochemical catalyst oxidation technology can directly utilize visible light or sunlight catalytic under the action of photochemical catalyst
Degrade VOCs, and it has the characteristics that environmentally protective, equipment requirement is low, reaction condition is mild and non-secondary pollution, becomes air
The mainstream technology of field of purification.Currently, in many visible light catalysts, Au-TiO2- CNTs (i.e. receive by gold-titanium dioxide-carbon
Mitron) because with excellent visible light catalytic performance and to the efficient adsorption capacities of VOCs, having in air purification field very big
Hair Zhang Qianli.
In the prior art, Au-TiO2The preparation process of-CNTs composite photo-catalysts is complex, and the knot of three kinds of ingredients
More difficult to control, easy influence photocatalysis effect is closed, while also needing to a large amount of toxic organic solvents of consumption and mould in preparation process
Plate agent (such as J.Li, S.B.Tang, L.Lu, et al.J.Am.Chem.Soc.2007,129,9401；Y.X.Zhang,B.Gao,
G.L.Puma, et al.Sci.Adv.Mater.2010,2,503), this can not only increase cost, but also can be produced to ecological environment
Raw secondary hazards.Therefore, it develops simple, effective and harmless preparation method and has become this field urgent problem to be solved.
Invention content
In view of this, the purpose of the present invention is to provide a kind of titanium dioxide of decorated by nano-gold-carbon nanotube complex lights
The preparation method of catalyst, preparation method provided by the invention can greatly simplify preparation process, composite photo-catalyst obtained
In conjunction with stabilization, with excellent catalytic degradation effect, and preparation process is without using toxic organic solvent and template, greatly
Width reduces cost and the harm to environment.
The present invention provides a kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst,
Include the following steps：
A) it using the aqueous solution of alcohol and steady-state gas as medium, is handled using micro-nano bubble generator, obtains micro-nano bubble water；
B) micro-nano bubble water, carbon nanotube and titanium salt are mixed and is disperseed, obtain dispersion liquid；
C) dispersion liquid mixed with ammonia spirit, hydrolyzed, obtain hydrolysate；
D) after mixing the hydrolysate with gold salt, micro-nano bubble water, photoreduction is carried out successively and heating is reacted, is obtained
To reaction product；
E) reaction product is heat-treated, obtains Au-TiO2- CNTs composite photo-catalysts.
Preferably, in the step a), the operating pressure of the micro-nano bubble generator is 0.25~0.65MPa, stable state
The air inflow of gas is 1.5~4.5L/min, and the aqueous solution of alcohol is 5~10L.
Preferably, in the step a), the alcohol in the aqueous solution of the alcohol includes one kind or several in ethyl alcohol and glycerine
Kind；
The mass concentration of the aqueous solution of the alcohol is 1%~50%；
The steady-state gas includes air, N2、O2、CO2And H2One or more of.
Preferably, in the step b), the ratio between the quality of carbon nanotube and the mole of titanium salt are (12~119) mg: (2
~10) mmol；
The volume of the micro-nano bubble water and the mass ratio of carbon nanotube are (40~120) mL: (12~119) mg.
Preferably, in the step c), the mass concentration of the ammonia spirit is 1%~5%；
The additive amount for controlling the ammonia spirit is collosol state occur to mixed liquor.
Preferably, in the step c), time of the hydrolysis is 8~for 24 hours.
Preferably, in the step d), the ratio between the volume of the micro-nano bubble water and the mole of gold salt are 10mL:
(0.004~0.032) mmol；
The gold salt and the molar ratio of titanium salt in step b) are (0.004~0.032): (2~10).
Preferably, in the step d), the power of the illumination is 10~300W, time of the photoreduction is 5~
15min；
The temperature of the heating reaction is 25~90 DEG C, and the time is 4~20h.
Preferably, in the step e), the temperature of the heat treatment is 200~450 DEG C, and the time is 1.5~3h.
Preferably, the carbon nanotube is multi-walled carbon nanotube；The caliber of the multi-walled carbon nanotube is 8~60nm；
The titanium salt is selected from TiCl4And TiOSO4One or more of；
The gold salt is selected from AuCl3And HAuCl4One or more of.
The present invention provides a kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst,
Include the following steps：A) it using the aqueous solution of alcohol and steady-state gas as medium, is handled using micro-nano bubble generator, obtains micro-nano gas
It is soaked；B) micro-nano bubble water, carbon nanotube and titanium salt are mixed and is disperseed, obtain dispersion liquid；C) by the dispersion liquid and ammonia
Aqueous solution mixing, hydrolysis, obtain hydrolysate；D) it after mixing the hydrolysate with gold salt, micro-nano bubble water, carries out successively
Photoreduction and heating are reacted, and reaction product is obtained；E) reaction product is heat-treated, obtains Au-TiO2- CNTs is multiple
Closing light catalyst.Compared with the prior art, provided by the invention preparation method is simple, enormously simplifies preparation process；And
Composite photo-catalyst obtained, which combines, to be stablized, and has effective and excellent catalytic degradation effect；Meanwhile preparation process without using
Toxic organic solvent and template significantly reduce cost and the harm to environment.Test result shows produced by the present invention
Au-TiO2- CNTs composite photo-catalysts are after the supersound process of 2h, nanometer Au and TiO2Particle is not from carbon due to ultrasonic disperse
Nanotube is removed, and has close interfacing relationship；Under illumination simulation, gained Au-TiO2- CNTs composite photo-catalysts are to benzene second
Alkene has excellent adsorption rate, degradation rate and mineralization rate, generates excellent catalytic degradation effect.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is 1 gained Au-TiO of embodiment2The scanning electron microscope (SEM) photograph of-MWCNTs composite photo-catalysts；
Fig. 2 is the transmission electron microscope picture of sample after the processing of 1 ultrasonic disperse of embodiment；
Fig. 3 is TiO2、Au-TiO2With 1 gained Au-TiO of embodiment2The Raman spectrum compares figure of-MWCNTs；
Fig. 4 is 2 gained Au-TiO of embodiment2The catalytic degradation curve graph of-MWCNTs composite photo-catalysts to styrene.
Specific implementation mode
The present invention provides a kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst,
Include the following steps：
A) it using the aqueous solution of alcohol and steady-state gas as medium, is handled using micro-nano bubble generator, obtains micro-nano bubble water；
B) micro-nano bubble water, carbon nanotube and titanium salt are mixed and is disperseed, obtain dispersion liquid；
C) dispersion liquid mixed with ammonia spirit, hydrolyzed, obtain hydrolysate；
D) after mixing the hydrolysate with gold salt, micro-nano bubble water, photoreduction is carried out successively and heating is reacted, is obtained
To reaction product；
E) reaction product is heat-treated, obtains Au-TiO2- CNTs composite photo-catalysts.
The present invention is using micro-nano bubble water as soft template, in conjunction with above-mentioned specific processing procedure, by titanium salt, gold salt raw material and
Carbon nanotube carrier induces synthetic technology, primary reconstruction and photo-reduction by micro-nano bubble interface charge by obtains Au-
TiO2- CNTs composite photo-catalysts, above-mentioned preparation process is simple and practicable, gained Au-TiO2- CNTs composite photo-catalysts have steady
Determine interfacial structure, show high visible-light activity and catalytic degradation, meanwhile, above-mentioned preparation process without toxic organic solvent and
Template significantly reduces cost and the harm to environment.
It is handled, is obtained using micro-nano bubble generator first using the aqueous solution of alcohol and steady-state gas as medium according to the present invention
Micro-nano bubble water.
The present invention carries out micro-nano processing using micro-nano generator to gas-liquid medium, forms micro-nano bubble water.Wherein, the alcohol
Aqueous solution in alcohol preferably include one or more of ethyl alcohol and glycerine.The mass concentration of the aqueous solution of the alcohol is preferred
It is 1%~50%.The usage amount of the aqueous solution of the alcohol is preferably 5~10L.
The steady-state gas preferably includes air, N2、O2、CO2And H2One or more of.The steady-state gas into
Tolerance is preferably 1.5~4.5L/min.
When the present invention carries out micro-nano processing using micro-nano generator to gas-liquid medium, the operating pressure of micro-nano generator is preferred
For 0.25~0.65MPa.Handled under the operating pressure using above-mentioned gas-liquid medium, be conducive to obtain bubble size and
Away from ideal, it is suitable for the micro-nano bubble water of template of the present invention, using the unique micro-nano bubble water as soft template, at this
In invention preparation system, special interface negative charge characteristic and the compatibility etc. to solid phase interface can be generated, in conjunction with this
The particular process of invention can effectively facilitate the high price cation such as Ti in raw material4+And Au3+In carbon nano tube surface pre-suction
Self assembly is echoed, Au is in TiO for control accurate nanometer2Position is modified in the space of-CNTs, and then acquisition has for interior typical case VOCs
Selective absorption, degradation visible light catalytic material.
According to the present invention, after obtaining micro-nano bubble water, micro-nano bubble water, carbon nanotube and titanium salt is mixed and disperseed, is obtained
To dispersion liquid.
In the present invention, the carbon nanotube is preferably multi-walled carbon nanotube (i.e. MWCNTs).The multi-walled carbon nanotube
Caliber is preferably 8~60nm.The purity of the multi-walled carbon nanotube is preferably >=90%.
In the present invention, the titanium salt is preferably TiCl4And TiOSO4One or more of.
In the present invention, the ratio between the quality of the carbon nanotube and the mole of titanium salt are preferably (12~119) mg: (2~
10) mmol makes carbon nanotube and TiO2Mass ratio be 4%~37%.
In the present invention, the volume of the micro-nano bubble water and the mass ratio of carbon nanotube are preferably (40~120) mL: (12
~119) mg.
It is preferably ultrasonic disperse by the mode that micro-nano bubble water, carbon nanotube and titanium salt mix dispersion in the present invention.This hair
In bright, the time of the mixing dispersion is preferably 15~40min.The present invention does not have special limit to the temperature of the mixing dispersion
System carries out, at room temperature such as in 25~30 DEG C of progress under room temperature.After mixing dispersion, dispersion liquid is obtained.
According to the present invention, after obtaining dispersion liquid, the dispersion liquid is mixed with ammonia spirit, is hydrolyzed, obtains hydrolysis production
Object.
In the present invention, the mass concentration of the ammonia spirit is preferably 1%~5%.Dispersion liquid is mixed with ammonia spirit
When, the additive amount for preferably controlling ammonia spirit is collosol state occur to mixed liquor.In some embodiments, ammonia spirit is controlled
Additive amount be the dispersion liquid 8%~40%, so that mixed liquor colloidal sol is occurred under the dosage.Present invention preferably employs to
The mode that ammonia spirit is added dropwise in dispersion liquid mixes the two, and ammonia spirit is added dropwise to stopping being added dropwise when there is collosol state, divides
Dispersion liquid and the ammonia spirit of dropwise addition continue hydrolysis.In the present invention, time of the hydrolysis is preferably 8~for 24 hours.This hair
The bright temperature to the mixing, hydrolysis is not particularly limited, and is carried out at room temperature, such as under room temperature at 25~30 DEG C
It carries out, after the hydrolysis, obtains hydrolysate.
According to the present invention, after obtaining hydrolysate, after the hydrolysate is mixed with gold salt, micro-nano bubble water, according to
Secondary progress photoreduction and heating are reacted, and reaction product is obtained.
In the present invention, the gold salt is preferably AuCl3And HAuCl4One or more of.The gold salt and abovementioned steps
The molar ratio of middle titanium salt is preferably (0.004~0.032): (2~10).
In the present invention, consistent described in the micro-nano bubble water and above-mentioned technical proposal, details are not described herein.The micro-nano
The ratio between the volume of air-bubble and the mole of gold salt are preferably 10mL: (0.004~0.032) mmol.
The mode that the present invention mixes hydrolysate with gold salt, micro-nano bubble water is not particularly limited, and can mix three
It closes uniform.In the present invention, the sequence that hydrolysate is mixed with gold salt, micro-nano bubble water is preferably first by gold salt and micro-nano gas
Soaked mixing obtains the micro-nano bubble aqueous solution of gold salt-containing, then is mixed with above-mentioned hydrolysate.
After three is mixed, photoreduction is first carried out.In the present invention, the photoreduction is preferably in visible light or ultraviolet light
According to lower progress, lamp source irradiation can be used, the light source is provided.In the present invention, the power of the illumination is preferably 10~300W.Institute
The time for stating photoreduction is preferably 5~15min.
After the photoreduction, heating reaction is also carried out.In the present invention, the temperature of the heating reaction is preferably 25~
90℃.The time of the heating reaction is preferably 4~20h.The mode of the heating is not particularly limited, in one embodiment
In, using oil bath heating.After heating reaction, reaction product is obtained.
The present invention carries out titanium salt hydrolysis and gold salt reduction successively using micro-nano bubble water as soft template, can effectively facilitate
TiO2Nano-particle and Au nano-particles, while can control accurate nanometer Au in carbon nano tube surface self assembly and Crystal nucleation
Space decorating site.
According to the present invention, after obtaining reaction product, the reaction product is heat-treated, Au-TiO is obtained2-CNTs
Composite photo-catalyst.
In the present invention, before being heat-treated to reaction product, preferably also it is freeze-dried.The item of the freeze-drying
Part is not particularly limited, and is this field conventional treatment.After the freeze-drying, it is heat-treated.
In the present invention, the temperature of the heat treatment is preferably 200~450 DEG C.The time of the heat treatment is preferably 1.5~
3h.Reaction product obtained by aforementioned treatment Step of the present invention is further heat-treated, interface cohesion stabilization, knot can be obtained
The firm Au-TiO of structure2- CNTs composite photo-catalysts.
The present invention provides a kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst,
Compared with the prior art, provided by the invention preparation method is simple, enormously simplifies preparation process；And complex light obtained
Catalyst, which combines, to be stablized, and has effective and excellent catalytic degradation effect；Meanwhile preparation process is without using toxic organic molten
Agent and template significantly reduce cost and the harm to environment.Test result shows Au-TiO produced by the present invention2-CNTs
Composite photo-catalyst is after the supersound process of 2h, nanometer Au and TiO2Particle is removed not due to ultrasonic disperse from carbon nanotube,
With close interfacing relationship；Under illumination simulation, gained Au-TiO2- CNTs composite photo-catalysts have styrene excellent
Adsorption rate, degradation rate and mineralization rate generate excellent catalytic degradation effect.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention
Limitation.It is raw materials used to be commercially available in following embodiment, wherein the caliber of multi-walled carbon nanotube is 8~60nm, purity is >=
90%.
Embodiment 1
The preparation of 1.1 samples
Using the ethanol water of 8L a concentration of 11% and air as medium, the micro-nano equipped with the micro-nano nozzle of high pressure is utilized
Rice bubble generator is handled, operating pressure 0.40MPa, and the air inflow of air is 1.5L/min, and micro-nano is obtained after processing
Air-bubble.80mL micro-nano bubble waters are taken to be placed in 250mL conical flasks, according to mass ratio MWCNTs：TiO2=26% upwards in turn
State MWCNTs the and 4mmol TiCl that 83.2mg is added in micro-nano bubble water4, conical flask is placed in ultrasonoscope and is ultrasonically treated
15min obtains uniform dispersion.A concentration of 2.6% dilute ammonia solution is gradually added dropwise into above-mentioned dispersion liquid to there is colloidal sol
Then state continues hydrolysis 13h at 30 DEG C of room temperature, obtains hydrolysate.It is added and contains into gained hydrolysate
0.018mmol HAuCl4Micro-nano bubble aqueous solution 10mL, irradiate 12min under 300W xenon sources, be subsequently placed in oil bath
12h is reacted at 70 DEG C, obtains black gray expandable reaction product.After gained black gray expandable reaction product is freeze-dried, forged at 420 DEG C
Heat preservation 2h is burnt, Au-TiO is obtained2- MWCNTs composite photo-catalysts.
The characterization of 1.2 samples and performance test
To gained Au-TiO2- MWCNTs composite photo-catalysts carry out microscopic appearance characterization, are as a result this referring to Fig. 1, Fig. 1
Au-TiO obtained by embodiment2The scanning electron microscope (SEM) photograph of-MWCNTs composite photo-catalysts, it can be seen that Au nano particles and TiO2Nanometer
Particle is uniformly distributed on one-dimensional MWCNTs carriers, and forms fine and close composite construction with MWCNTs.
By gained Au-TiO2- MWCNTs composite photo-catalysts are placed in ultrasonic disperse in ethanol system and handle 2h, utilize transmission
Electronic Speculum observes sample after decentralized processing, and the results are shown in Figure 2, and Fig. 2 is the transmission electricity of sample after the processing of the present embodiment ultrasonic disperse
Mirror figure, it can be seen that after the decentralized processing of 2h, Au nano particles and TiO2Nano particle is still closely tied with MWCNTs carriers
It closes, is not peeled away because of ultrasonic disperse；It may be speculated that Au/TiO2Chemical bond has been likely to form between MWCNTs.Gained
Au-TiO2In-MWCNTs composite photo-catalysts, Au/TiO2With the close interfacing relationships of MWCNTs, it is very beneficial for light induced electron
By Au/TiO2Surface is transferred to MWCNTs, and then improves the separative efficiency and photocatalysis efficiency of photo-generated carrier.
To gained Au-TiO2- MWCNTs composite photo-catalysts, TiO2 and Au-TiO2Raman spectrum test, knot are carried out respectively
Fruit is as shown in figure 3, Fig. 3 is TiO2、Au-TiO2With Au-TiO obtained by the present embodiment2Raman spectrum compares figure (Fig. 3 of-MWCNTs
Middle Au/TiO2@CNTs are Au-TiO2- MWCNTs, Au/TiO2As Au-TiO2), Au-TiO in figure2- MWCNTs complex lights
The offset of the characteristic peak of catalyst further proves Au/TiO2Chemical bond is formd between MWCNTs.
Under simulated solar illumination, gained Au-TiO is utilized2- MWCNTs composite photo-catalysts carry out the catalysis to styrene
Degradation test, the results show that Au-TiO2- MWCNTs composite photo-catalysts have stronger degradation and mineralization ability to styrene,
It reaches 80% to the highest adsorption rate of styrene, in continuous degradation 300min, stablizes to the degradation efficiency of styrene
75%, trend is not decreased significantly, 50% has been reached to the mineralising efficiency of styrene, gained photochemical catalyst can effectively promote
The synthesis speed for making oxyradical such as hydroxyl radical free radical and superoxide radical effectively facilitates the benzene for being enriched in photocatalyst surface
The degradation of ethylene and mineralising, while the problems such as avoid product accumulation, catalyst inactivation caused by interfacial mass transfer problem.
Embodiment 2
The preparation of 1.1 samples
Using the ethanol water of 8L a concentration of 11% and air as medium, the micro-nano equipped with the micro-nano nozzle of high pressure is utilized
Rice bubble generator is handled, operating pressure 0.40MPa, and the air inflow of air is 3L/min, and micro-nano gas is obtained after processing
It is soaked.80mL micro-nano bubble waters are taken to be placed in 250mL conical flasks, according to mass ratio MWCNTs：TiO2=26% states upwards in turn
MWCNTs the and 4mmol TiCl of 83.2mg are added in micro-nano bubble water4, conical flask is placed in ultrasonoscope and is ultrasonically treated
15min obtains uniform dispersion.A concentration of 2.6% dilute ammonia solution is gradually added dropwise into above-mentioned dispersion liquid to there is colloidal sol
Then state continues hydrolysis 13h at 30 DEG C of room temperature, obtains hydrolysate.It is added and contains into gained hydrolysate
0.018mmol HAuCl4Micro-nano bubble aqueous solution 10mL, irradiate 12min under 300W xenon sources, be subsequently placed in oil bath
12h is reacted at 90 DEG C, obtains black gray expandable reaction product.After gained black gray expandable reaction product is freeze-dried, forged at 420 DEG C
Heat preservation 2h is burnt, Au-TiO is obtained2- MWCNTs composite photo-catalysts.
The characterization of 1.2 samples and performance test
According to the characterizing method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out microscopic appearance table
Sign, the results show that Au nano particles and TiO2Nano particle is uniformly distributed on one-dimensional MWCNTs carriers, and is formed with MWCNTs
Fine and close composite construction.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out ultrasonic disperse processing
And sample after inspection process, the results show that after the decentralized processing of 2h, Au nano particles and TiO2Nano particle still with
MWCNTs carriers are combined closely, and are not peeled away because of ultrasonic disperse, Au/TiO2Nano particle is formed surely with MWCNTs carriers
It is fixed, firm to combine.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts urge styrene
Change degradation test, the results are shown in Figure 4, and Fig. 4 is Au-TiO obtained by the present embodiment2- MWCNTs composite photo-catalysts are to styrene
Catalytic degradation curve graph.It can be seen that Au-TiO2- MWCNTs composite photo-catalysts to styrene have it is stronger degradation and
Mineralization ability has reached 81.4%, in continuous degradation 300min, to the drop of styrene to the highest adsorption rate of styrene
Stabilised efficiency is solved 80%, trend is not decreased significantly, 72.3% relatively Gao Shui has been reached to the mineralising efficiency of styrene
Flat, gained photochemical catalyst can effectively promote the synthesis speed of oxyradical such as hydroxyl radical free radical and superoxide radical, effectively
Promote the degradation and the mineralising that are enriched in the styrene of photocatalyst surface, while avoiding the product caused by interfacial mass transfer problem
The problems such as accumulation, catalyst inactivation.
Embodiment 3
The preparation of 1.1 samples
Using the ethanol water of 8L a concentration of 11% and air as medium, the micro-nano equipped with the micro-nano nozzle of high pressure is utilized
Rice bubble generator is handled, operating pressure 0.40MPa, and the air inflow of air is 3L/min, and micro-nano gas is obtained after processing
It is soaked.80mL micro-nano bubble waters are taken to be placed in 250mL conical flasks, according to mass ratio MWCNTs：TiO2=4.04% upwards in turn
State MWCNTs the and 4mmol TiOSO that 12.8mg is added in micro-nano bubble water4, conical flask is placed in ultrasonoscope and is ultrasonically treated
30min obtains uniform dispersion.A concentration of 2.6% dilute ammonia solution is gradually added dropwise into above-mentioned dispersion liquid to there is colloidal sol
Then state continues hydrolysis 13h at 30 DEG C of room temperature, obtains hydrolysate.It is added and contains into gained hydrolysate
0.004mmol HAuCl4Micro-nano bubble aqueous solution 10mL, irradiate 12min under 300W xenon sources, be subsequently placed in oil bath
12h is reacted at 85 DEG C, obtains black gray expandable reaction product.After gained black gray expandable reaction product is freeze-dried, forged at 420 DEG C
Heat preservation 2h is burnt, Au-TiO is obtained2- MWCNTs composite photo-catalysts.
The characterization of 1.2 samples and performance test
According to the characterizing method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out microscopic appearance table
Sign, the results show that Au nano particles and TiO2Nano particle is uniformly distributed on one-dimensional MWCNTs carriers, and is formed with MWCNTs
Fine and close composite construction.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out ultrasonic disperse processing
And sample after inspection process, the results show that after the decentralized processing of 2h, Au nano particles and TiO2Nano particle still with
MWCNTs carriers are combined closely, and are not peeled away because of ultrasonic disperse, Au/TiO2Nano particle is formed surely with MWCNTs carriers
It is fixed, firm to combine.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts urge styrene
Change degradation test, the results show that Au-TiO2- MWCNTs composite photo-catalysts have stronger degradation and mineralising energy to styrene
Power reaches 78% to the highest adsorption rate of styrene, in continuous degradation 300min, stablizes to the degradation efficiency of styrene
77%, trend is not decreased significantly, 45% has been reached to the mineralising efficiency of styrene, gained photochemical catalyst can be effective
The synthesis speed for promoting oxyradical such as hydroxyl radical free radical and superoxide radical, effectively facilitates and is enriched in photocatalyst surface
The degradation of styrene and mineralising, while the problems such as avoid product accumulation, catalyst inactivation caused by interfacial mass transfer problem.
Embodiment 4
The preparation of 1.1 samples
Using the ethanol water of 8L a concentration of 16% and air as medium, the micro-nano equipped with the micro-nano nozzle of high pressure is utilized
Rice bubble generator is handled, operating pressure 0.40MPa, and the air inflow of air is 3L/min, and micro-nano gas is obtained after processing
It is soaked.80mL micro-nano bubble waters are taken to be placed in 250mL conical flasks, according to mass ratio MWCNTs：TiO2=15% states upwards in turn
MWCNTs the and 4mmol TiCl of 48mg are added in micro-nano bubble water4, conical flask is placed in ultrasonoscope and is ultrasonically treated
15min obtains uniform dispersion.A concentration of 2.6% dilute ammonia solution is gradually added dropwise into above-mentioned dispersion liquid to there is colloidal sol
Then state continues hydrolysis 13h at 30 DEG C of room temperature, obtains hydrolysate.It is added and contains into gained hydrolysate
0.018mmol HAuCl4Micro-nano bubble aqueous solution 10mL, irradiate 12min under 300W xenon sources, be subsequently placed in oil bath
12h is reacted at 55 DEG C, obtains black gray expandable reaction product.After gained black gray expandable reaction product is freeze-dried, forged at 420 DEG C
Heat preservation 2h is burnt, Au-TiO is obtained2- MWCNTs composite photo-catalysts.
The characterization of 1.2 samples and performance test
According to the characterizing method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out microscopic appearance table
Sign, the results show that Au nano particles and TiO2Nano particle is uniformly distributed on one-dimensional MWCNTs carriers, and is formed with MWCNTs
Fine and close composite construction.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts carry out ultrasonic disperse processing
And sample after inspection process, the results show that after the decentralized processing of 2h, Au nano particles and TiO2Nano particle still with
MWCNTs carriers are combined closely, and are not peeled away because of ultrasonic disperse, Au/TiO2Nano particle is formed surely with MWCNTs carriers
It is fixed, firm to combine.
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite photo-catalysts urge styrene
Change degradation test, the results show that Au-TiO2- MWCNTs composite photo-catalysts have stronger degradation and mineralising energy to styrene
Power reaches 75% to the highest adsorption rate of styrene, in continuous degradation 300min, stablizes to the degradation efficiency of styrene
74%, trend is not decreased significantly, 52% has been reached to the mineralising efficiency of styrene, gained photochemical catalyst can be effective
The synthesis speed for promoting oxyradical such as hydroxyl radical free radical and superoxide radical, effectively facilitates and is enriched in photocatalyst surface
The degradation of styrene and mineralising, while the problems such as avoid product accumulation, catalyst inactivation caused by interfacial mass transfer problem.
Comparative example 1
The preparation of 1.1 samples
Multi-walled carbon nanotube (MWCNTs) and lauryl sodium sulfate are scattered in 10mL aqueous solutions, wherein MWCNTs
A concentration of 14.5mg/mL, a concentration of 5mg/mL of lauryl sodium sulfate form suspension；Gained suspension is scattered in 20mL
In absolute ethyl alcohol, 30min is stirred, Solution I is obtained.4.45mol titanium isopropoxides, 15mL ethyl alcohol and 0.1mL acetic acid are mixed
Stirring is closed, clear solution Solution II is formed.Under magnetic stirring, above-mentioned Solution I is added drop-wise to Solution dropwise
In II, after being stirred to react 2h, the PH that the ammonia spirit of 1mol/L adjusts mixed liquor is used to add 10mL ethyl alcohol and continue to stir for 9
Mix 30min；Products therefrom is centrifuged, is subsequently placed in 60 DEG C of baking ovens and dries 10h, obtains the first product, in product
MWCNTs and TiO2Mass ratio be 0.4.
Chlorauric acid solution (3mL, 32.85mM) is added in the toluene solution of ammonium bromide and tetraoctyl ammonium bromide (3.982mL,
49.5mM), solution is become colorless by yellow, and the toluene solution (0.4455mL, 0.1106M) of lauryl mercaptan is added thereto, stirs
Processing 15min is mixed to be washed with ethyl alcohol after drying products therefrom organic phase (about 4.43mL) at room temperature using vacuum desiccator
It washs, obtains the second product (the Au nano particles of 2~3nm).
The 3- mercaptopropionic acids (0.22M) of the first product of gained and 1mL are scattered in 4mL toluene, 2h is ultrasonically treated, obtains
First dispersion liquid；The second product of gained is scattered in 2mL toluene, the second dispersion liquid is obtained；With vigorous stirring, by second point
Dispersion liquid is added drop-wise to dropwise in the second dispersion liquid, continues after stirring 5h, a nanometer Au is made to be attached to TiO2On/CNTs, washed with acetone
Three times, be dried overnight at normal temperatures, be placed in tube furnace, be warming up to 500 DEG C with 10 DEG C/min, keep the temperature 30min, obtain
Au-TiO2- MWCNTs nanocomposites.
The performance test of 1.2 samples
According to the test method of embodiment 1 to gained Au-TiO2- MWCNTs composite materials carry out the drop of the catalysis to styrene
Solution test, the results show that gained Au-TiO2Although-MWCNTs composite materials can reach and this hair the adsorption rate of styrene
The bright comparable level of embodiment, but it is obviously deteriorated to the degradation of styrene and mineralization ability, in continuous degradation 300min,
It is only finally 24.5% to the degradation efficiency of styrene, and decreased significantly trend, only also not to the mineralising efficiency of styrene
To 1%, gained composite material exhibits go out poor Photocatalytic Degradation Property.
By testing effect above it is found that compared with the prior art, preparation method provided by the invention enormously simplifies preparation
Process, and the use of toxic organic solution and template is avoided, moreover, Au-TiO produced by the present invention2- MWCNTs is compound
Photochemical catalyst has stable, firm structure and nanometer Au, and accurately space is modified, and then shows better photocatalysis drop
Solve effect.
Principle and implementation of the present invention are described for specific case used herein, and above example is said
The bright method and its core concept for being merely used to help understand the present invention, including best mode, and but also this field is appointed
What technical staff can put into practice the present invention, including manufacture and use any device or system, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, these improvement and modification are also fallen within the protection scope of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementation
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, are wanted then these other embodiments should also be included in right
In the range of asking.
Claims (10)
1. a kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst, which is characterized in that including
Following steps：
A) it using the aqueous solution of alcohol and steady-state gas as medium, is handled using micro-nano bubble generator, obtains micro-nano bubble water；
B) micro-nano bubble water, carbon nanotube and titanium salt are mixed and is disperseed, obtain dispersion liquid；
C) dispersion liquid mixed with ammonia spirit, hydrolyzed, obtain hydrolysate；
D) after mixing the hydrolysate with gold salt, micro-nano bubble water, photoreduction is carried out successively and heating is reacted, is obtained anti-
Answer product；
E) reaction product is heat-treated, obtains Au-TiO2- CNTs composite photo-catalysts.
2. preparation method according to claim 1, which is characterized in that in the step a), the micro-nano bubble generator
Operating pressure be 0.25~0.65MPa, the air inflow of steady-state gas is 1.5~4.5L/min, and the aqueous solution of alcohol is 5~10L.
3. preparation method according to claim 1 or 2, which is characterized in that in the step a), the aqueous solution of the alcohol
In alcohol include one or more of ethyl alcohol and glycerine；
The mass concentration of the aqueous solution of the alcohol is 1%~50%；
The steady-state gas includes air, N2、O2、CO2And H2One or more of.
4. preparation method according to claim 1, which is characterized in that in the step b), the quality and titanium of carbon nanotube
The ratio between mole of salt is (12~119) mg: (2~10) mmol；
The volume of the micro-nano bubble water and the mass ratio of carbon nanotube are (40~120) mL: (12~119) mg.
5. preparation method according to claim 1, which is characterized in that in the step c), the quality of the ammonia spirit
A concentration of 1%~5%；
The additive amount for controlling the ammonia spirit is collosol state occur to mixed liquor.
6. preparation method according to claim 1 or 5, which is characterized in that in the step c), the time of the hydrolysis is
8~for 24 hours.
7. preparation method according to claim 1, which is characterized in that in the step d), the body of the micro-nano bubble water
The ratio between product and the mole of gold salt are 10mL: (0.004~0.032) mmol；
The gold salt and the molar ratio of titanium salt in step b) are (0.004~0.032): (2~10).
8. preparation method according to claim 1 or claim 7, which is characterized in that in the step d), the power of the illumination is
The time of 10~300W, the photoreduction are 5~15min；
The temperature of the heating reaction is 25~90 DEG C, and the time is 4~20h.
9. preparation method according to claim 1, which is characterized in that in the step e), the temperature of the heat treatment is
200~450 DEG C, the time is 1.5~3h.
10. preparation method according to claim 1, which is characterized in that the carbon nanotube is multi-walled carbon nanotube；It is described
The caliber of multi-walled carbon nanotube is 8~60nm；
The titanium salt is selected from TiCl4And TiOSO4One or more of；
The gold salt is selected from AuCl3And HAuCl4One or more of.
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