CN107376912A - A kind of multilayer TiO2Nanotube based photocatalyst and preparation method and application - Google Patents
A kind of multilayer TiO2Nanotube based photocatalyst and preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 57
- 239000002071 nanotube Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 113
- 238000013019 agitation Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 38
- 235000019441 ethanol Nutrition 0.000 claims description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 229910002367 SrTiO Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000007788 liquid Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 first Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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- 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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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a kind of multilayer TiO2Nanotube based photocatalyst and preparation method and application.Photochemical catalyst is TN@SrTiO3@Ag@Bi2O3@Ag, every layer of Ag mass fraction 0.5%, SrTiO3For 1%, Bi2O3For 1%.Preparation method is as follows：1）By TiO2Nanotube is put in calcining in Muffle furnace and obtains Detitanium-ore-type TN；2）TN is dispersed in Sr (OH) by stirring2In solution, then hydro-thermal process obtains TN@SrTiO3；3）By stirring TN@SrTiO3It is dispersed in AgNO3In solution, then by Microwave Water it is thermally treated resulting in TN SrTiO3@Ag；4）By stirring TN@SrTiO3@Ag are dispersed in Bi (NO3)3In solution, subsequent microwave hydrothermal processing, washing, dry, calcination processing；5）According to 3）Middle method is by TN@SrTiO3@Ag@Bi2O3With AgNO3Solution hydro-thermal reaction obtains.Noble metal loading between the two layers, is regulated and controled, accelerates electron transfer rate, reduce the compound of photo-generated carrier by the photochemical catalyst of the present invention by Ag interface.The hetero-junctions formed simultaneously has not only widened photoresponse scope, and enhances light absorpting ability, shows excellent photocatalysis performance.
Description
Technical field
The present invention relates to a kind of multilayer TiO for light-catalyzed reaction2Nanotube sill and preparation method thereof, belongs to light
Catalysis material and environmental protection technical field.
Background technology
With industrial expansion, problem of environmental pollution is on the rise, and the discharge capacity of outdoor waste gas is increasing, while indoor
Air pollution problems inherent also can not be ignored, how preferably to handle these waste gas turns into urgent problem to be solved.Photocatalytic degradation
Technology because of course of reaction rapidly and efficiently, the advantages that energy consumption is low, non-secondary pollution, turn into one of most promising technology.But still deposit
In some defects, traditional photochemical catalyst such as TiO2Forbidden band it is wide, only to ultraviolet light response, and electronics and hole are easily compound, cause
Photocatalytic activity and efficiency reduce.Therefore efficient TiO is constructed2The research and development and utilization of photochemical catalyst are always in photocatalysis field
Primary study object.TN@SrTiO3@Ag@Bi2O3@Ag are in TiO2SrTiO is sequentially depositing on the basis of nanotube3、Ag、
Bi2O3, Ag and formed.1-dimention nano tubular construction can promote the capture ability to photon, be advantageous to accelerate the migration of electric charge and divide
From.SrTiO3Hole transmission layer can be served as, effectively suppresses the compound of TN photo-generated carriers.Simultaneously by noble metal loading two layers it
Between, regulated and controled by Ag interface, accelerate electron transfer rate, the compound of photo-generated carrier is reduced, so as to improve photocatalysis efficiency.
Shuang Shuang et al. (Sci Rep.2016；6:26670.) a kind of TiO is proposed2The design of nano-array pipe.With Au and Pt
Nano-particle adsorbs and reacted directly synthesis at room temperature by continuous ionic layer.Significantly improve TiO2Photogenerated charge point
From, and then improve photocatalysis efficiency.Sunita Khanchandani et al. (J.Phys.Chem.C 2013,117,5558-
5567) it is prepared for ZnO/In2S3The nano-array of II type nucleocapsids.Core shell photochemical catalyst being capable of obvious light under visible light illumination
Catalytic degradation RhB, efficiency are higher than In2S3/ ZnO nanorod.The raising of catalytic activity is due to that the formation of two heterojunction semiconductors promotees
Make efficiently separating for photo-generate electron-hole.But the synthetic method of these composites, first, Au, Pt price is more in noble metal
Costliness, second, it is difficult the boundary for being formed and being separated beneficial to electronics and hole that fully interweaves that nanocomposite constituents are more single.
The content of the invention
For above-mentioned photocatalysis field, particularly TiO2Nanotube based photocatalyst problem encountered, the present invention provide
A kind of multilayer TiO2Nanotube based photocatalyst and preparation method thereof, and it is used for photocatalytic degradation organic exhaust gas.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of multilayer TiO2Nanotube based photocatalyst, the photochemical catalyst are by TiO2Nanotube does substrate, is sequentially depositing
SrTiO3、Ag、Bi2O3, Ag composition, counted using the weight of catalyst as 100%, every layer of Ag mass fraction 0.5%, SrTiO3's
Mass fraction is 1%, Bi2O3Mass fraction be 1%, surplus TiO2Nanotube.
Above-mentioned multilayer TiO2The preparation method of nanotube based photocatalyst, comprises the following steps：
(1) by TiO2Nanotube is put in the TiO that calcining is handled well in Muffle furnace2Nanotube；
(2) by TiO2Nanotube is dissolved in ethanol, magnetic agitation；Take Sr (OH)2It is dissolved in pure water, ultrasound makes its uniform；
TiO is added dropwise to again2In nanotube solution, magnetic agitation；Hydro-thermal afterwards, centrifuge washing are dried to obtain TN@SrTiO3；
(3) by TN@SrTiO3It is dissolved in ethanol and water volume ratio 1:In 1 solution, magnetic agitation；Take AgNO3Be dissolved in ethanol with
Water volume ratio 1:In 1 solution, ultrasound makes its uniform；TN@SrTiO are added dropwise to again3Magnetic agitation in solution；Microwave Water afterwards
Heat, centrifuge washing are dried to obtain TN@SrTiO3@Ag；
(4) by TN@SrTiO3@Ag are dissolved in ethanol, magnetic agitation；Take Bi (NO3)3It is dissolved in ethylene glycol and ethanol mixing is molten
In liquid, ultrasound makes its uniform；TN@SrTiO are added dropwise to again3Magnetic agitation in@Ag solution；Microwave hydrothermal afterwards, centrifuge washing
Dry, then calcine to obtain TN@SrTiO3@Ag@Bi2O3；
(5) according to method in step (3) in TN@SrTiO3@Ag@Bi2O3Upper redeposited one layer of Ag obtains TN SrTiO3@
Ag@Bi2O3@Ag。
Calcination process wherein described in step (1), refer to calcine 2~4h under the conditions of 350~500 DEG C.
The magnetic agitation time described in step (2) is 30~60min, hydrothermal condition be 180~240 DEG C of hydro-thermals 18~
30h, washing process refers to be washed several times with 0.05~0.2M acetic acid, then is washed several times with pure water and absolute ethyl alcohol.Drying process
Refer to 6~24h of freeze-day with constant temperature in 60~80 DEG C of air atmosphere.
The magnetic agitation time described in step (3) is 30~60min, microwave hydrothermal parameter：Temperature is 120~180 DEG C,
Time is 1~3h, and power is 300~500W.Washing process refers to be washed several times with pure water and absolute ethyl alcohol.Drying process refers to
6~24h of freeze-day with constant temperature in 60~80 DEG C of air atmosphere.
The magnetic agitation time described in step (4) is 30~60min, microwave hydrothermal parameter：Temperature is 120~180 DEG C,
Time is 1~3h, and power is 300~500W.Washing process refers to be washed several times with pure water and absolute ethyl alcohol.Drying process refers to
6~24h of freeze-day with constant temperature in 60~80 DEG C of air atmosphere.Calcination process refer in Muffle furnace 400~600 DEG C of calcinings 3~
5h。
It is also another object of the present invention to provide above-mentioned multilayer TiO2The application of nanotube based photocatalyst.
Multilayer TiO provided by the present invention2The application of nanotube based photocatalyst is it in room temperature visible light catalytic field
In application.The visible light catalyst all has certain catalytic effect to monomeric small molecule organic matter, empty available for degraded
Organic pollution in gas, such as formaldehyde, toluene.
Compared with prior art, the present invention has the advantages that:
The multilayer TiO that the present invention uses2The preparation method of nanotube based photocatalyst is microwave-hydrothermal method, 1-dimention nano pipe
Structure can promote the capture ability to photon, be advantageous to accelerate the migration and separation of electric charge.SrTiO3Hole transmission layer can be served as,
Effectively suppress the compound of TN photo-generated carriers.In addition Ag as a kind of noble metal uniform deposition between the two layers, pass through Ag boundary
Face regulates and controls, and accelerates electron transfer rate, reduces the compound of photo-generated carrier.Also deposition has Bi simultaneously2O3As compound phase component,
Multiphase hetero-junctions is formed, promotes the separation of photo-generate electron-hole, so as to improve light-catalyzed reaction efficiency.For Low Concentration Toluene,
, can be at ambient temperature by the almost complete oxygen of toluene, formaldehyde in system during the visible light catalytic reaction of the organic gas such as formaldehyde
Turn to carbon dioxide and water.Multilayer TiO2The preparation method mild condition of nanotube based photocatalyst, high catalytic efficiency, operation side
Just, it is easy to industry's enlarging production.
Brief description of the drawings
Fig. 1 is the sample TN@SrTiO prepared in each embodiment3@Ag@Bi2O3@Ag (TSABA), TN@Ag@SrTiO3@Ag
(TASA), TN@SrTiO3@Bi2O3@Ag (TSBA), TN@SrTiO3@Bi2O3(TSB) and TN@Ag (TA) uv-vis spectra pair
Than figure.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
A kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in Muffle furnace
In 400 DEG C of TiO for being handled well of calcining 2h2Nanotube；(2) by 0.30g TiO2Nanotube is dissolved in 20mL ethanol, and magnetic force stirs
Mix 30min.By 0.0044g Sr (OH)2It is dissolved in pure water, and adds TiO2In nanotube solution, then after magnetic agitation 30min,
200 DEG C of hydro-thermal 24h in autoclave are poured into, after naturally cooling to room temperature, are centrifugally separating to obtain solid, and it is molten with 0.1M acetic acid
Liquid is washed 2 times, and pure water and absolute ethyl alcohol are respectively washed 3 times, are put into 60 DEG C of baking oven freeze-day with constant temperature 10h and are obtained TN@SrTiO3；(3) will
0.30g TN@SrTiO3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, magnetic agitation 30min.By 0.0024g AgNO3
It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, and add TN@SrTiO3In solution, magnetic agitation 30min.150 DEG C of water
After hot 2h, with pure water and absolute ethyl alcohol respectively washing 3 times, it is put into 60 DEG C of baking oven freeze-day with constant temperature 10h and obtains TN@SrTiO3@Ag；(4)
By 0.30g TN@SrTiO3@Ag are dissolved in 20mL ethanol.By 0.0031g Bi (NO3)3It is dissolved in 20mL ethylene glycol and 20mL ethanol
In mixed solution, and add TN@SrTiO3In@Ag solution, after magnetic agitation 30min, 150 DEG C of hydro-thermal 2h, with pure water and anhydrous
Ethanol respectively washing 3 times, after being put into 60 DEG C of baking oven freeze-day with constant temperature 10h, 450 DEG C of calcining 3h obtain TN@SrTiO3@Ag@Bi2O3；(5)
According to method in (3) in TN@SrTiO3@Ag@Bi2O3Upper redeposited one layer of Ag obtains final products.
Comparative example 1
Contrast a kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in horse
The TiO that not 400 DEG C of calcining 2h are handled well in stove2Nanotube；(2) by 0.30g TiO2Nanotube is dissolved in 20mL ethanol, magnetic
Power stirs 30min.By 0.0044g Sr (OH)2It is dissolved in pure water, and adds TiO2In nanotube solution, then magnetic agitation 30min
Afterwards, 200 DEG C of hydro-thermal 24h in autoclave are poured into, after naturally cooling to room temperature, are centrifugally separating to obtain solid, and with 0.1M vinegar
Acid solution wash 2 times, pure water and absolute ethyl alcohol are respectively washed 3 times, are put into 60 DEG C of baking oven freeze-day with constant temperature 10h and are obtained TN@SrTiO3；(3)
By 0.30g TN@SrTiO3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, magnetic agitation 30min.By 0.0024g
AgNO3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, and add TN@SrTiO3In solution, magnetic agitation 30min.150
After DEG C hydro-thermal 2h, with pure water and absolute ethyl alcohol respectively washing 3 times, it is put into 60 DEG C of baking oven freeze-day with constant temperature 10h and obtains TN@SrTiO3@Ag；
(4) by 0.30g TN@SrTiO3@Ag are dissolved in 20mL ethanol.By 0.0031g Bi (NO3)3It is dissolved in 20mL ethylene glycol and 20mL second
In mixed alkoxide solution, and add TN@SrTiO3In@Ag solution, after magnetic agitation 30min, 150 DEG C of hydro-thermal 2h, with pure water and nothing
Water-ethanol respectively washing 3 times, after being put into 60 DEG C of baking oven freeze-day with constant temperature 10h, 450 DEG C of calcining 3h obtain final products.
Embodiment 2
A kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in Muffle furnace
In 400 DEG C of TiO for being handled well of calcining 2h2Nanotube；(2) 0.30g TN are dissolved in 20mL ethanol and water volume ratio 1:1
In solution, magnetic agitation 30min.By 0.0024g AgNO3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, and add
In TN solution, magnetic agitation 30min.After 150 DEG C of hydro-thermal 2h, with pure water and absolute ethyl alcohol respectively washing 3 times, 60 DEG C of baking oven perseverances are put into
Temperature dries 10h and obtains TN@Ag；(3) by stirring TN@Ag solution and Sr (OH)2Solution mixes, then obtains TN@by hydro-thermal
Ag@SrTiO30.30g TN@Ag are dissolved in 20mL ethanol, magnetic agitation 30min.By 0.0044g Sr (OH)2It is dissolved in pure water
In, and add in TN@Ag solution, then after magnetic agitation 30min, pour into 200 DEG C of hydro-thermal 24h, natural cooling in autoclave
To after room temperature, solid is centrifugally separating to obtain, and is washed 2 times with 0.1M acetums, pure water and absolute ethyl alcohol are respectively washed 3 times, are put into
60 DEG C of baking oven freeze-day with constant temperature 10h obtain TN@Ag@SrTiO3；(4) according to method in (2) in TN@Ag@SrTiO3Upper redeposited one layer
Ag obtains final products.
Embodiment 3
A kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in Muffle furnace
In 400 DEG C of TiO for being handled well of calcining 2h2Nanotube；(2) by 0.30g TiO2Nanotube is dissolved in 20mL ethanol, and magnetic force stirs
Mix 30min.By 0.0044g Sr (OH)2It is dissolved in pure water, and adds TiO2In nanotube solution, then after magnetic agitation 30min,
200 DEG C of hydro-thermal 24h in autoclave are poured into, after naturally cooling to room temperature, are centrifugally separating to obtain solid, and it is molten with 0.1M acetic acid
Liquid is washed 2 times, and pure water and absolute ethyl alcohol are respectively washed 3 times, are put into 60 DEG C of baking oven freeze-day with constant temperature 10h and are obtained TN@SrTiO3；(3) will
0.30g TN@SrTiO3It is dissolved in 20mL ethanol.By 0.0031g Bi (NO3)3It is dissolved in 20mL ethylene glycol and the mixing of 20mL ethanol is molten
In liquid, and add TN@SrTiO3In solution, after magnetic agitation 30min, 150 DEG C of hydro-thermal 2h, respectively washed with pure water and absolute ethyl alcohol
3 times, after being put into 60 DEG C of baking oven freeze-day with constant temperature 10h, 450 DEG C of calcining 3h obtain TN@SrTiO3@Bi2O3；(4) by 0.30g TN@
SrTiO3@Bi2O3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, magnetic agitation 30min.By 0.0024g AgNO3It is molten
In 20mL ethanol and water volume ratio 1:In 1 solution, and add TN@SrTiO3@Bi2O3In solution, magnetic agitation 30min.150
After DEG C hydro-thermal 2h, with pure water and absolute ethyl alcohol respectively washing 3 times, it is put into 60 DEG C of baking oven freeze-day with constant temperature 10h and obtains final products.
Embodiment 4
A kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in Muffle furnace
In 400 DEG C of TiO for being handled well of calcining 2h2Nanotube；(2) by 0.30g TiO2Nanotube is dissolved in 20mL ethanol, and magnetic force stirs
Mix 30min.By 0.0044g Sr (OH)2It is dissolved in pure water, and adds TiO2In nanotube solution, then after magnetic agitation 30min,
200 DEG C of hydro-thermal 24h in autoclave are poured into, after naturally cooling to room temperature, are centrifugally separating to obtain solid, and it is molten with 0.1M acetic acid
Liquid is washed 2 times, and pure water and absolute ethyl alcohol are respectively washed 3 times, are put into 60 DEG C of baking oven freeze-day with constant temperature 10h and are obtained TN@SrTiO3；(3) will
0.30g TN@SrTiO3It is dissolved in 20mL ethanol.By 0.0031g Bi (NO3)3It is dissolved in 20mL ethylene glycol and the mixing of 20mL ethanol is molten
In liquid, and add TN@SrTiO3In solution, after magnetic agitation 30min, 150 DEG C of hydro-thermal 2h, respectively washed with pure water and absolute ethyl alcohol
3 times, after being put into 60 DEG C of baking oven freeze-day with constant temperature 10h, 450 DEG C of calcining 3h obtain final products.
Embodiment 5
A kind of multilayer TiO2The preparation method of nanotube based photocatalyst：(1) by the TiO of purchase2Nanotube is put in Muffle furnace
In 400 DEG C of TiO for being handled well of calcining 2h2Nanotube；(2) 0.30g TN are dissolved in 20mL ethanol and water volume ratio 1:1
In solution, magnetic agitation 30min.By 0.0024g AgNO3It is dissolved in 20mL ethanol and water volume ratio 1:In 1 solution, and add
In TN solution, magnetic agitation 30min.After 150 DEG C of hydro-thermal 2h, with pure water and absolute ethyl alcohol respectively washing 3 times, 60 DEG C of baking oven perseverances are put into
Temperature dries 10h and obtains final products.
Embodiment 6
Catalyst described in taking 0.2g embodiments 1-5 respectively, with pure water as solvent, is uniformly applied to 7.0cm2Surface plate in
And dry, reactor bottom is placed in, with gaseous mixture (O2:N2=1:3) purge 20min and remove CO in reactor2.Toluene visible ray
Catalytic reaction experiment condition is：Pure toluene liquid is by bubbling, by gaseous mixture (O2:N2=1:3) reactor, control reaction are blown into
Toluene initial concentration is~400ppm in kettle, and relative humidity is~18%, and lucifuge is handled reactor at room temperature before illumination
20min, toluene is set to reach adsorption-desorption balance in catalyst surface.Load onto total reflection piece and filter ultraviolet reflector plate, use
200w xenon lamp is as simulated visible light source (λ=420~780nm, light intensity 150mwcm-2), 5h is reacted, is taken every 30min
Sample, toluene concentration is detected by gas-chromatography (GC7900, FID) and (GC2060, FID) detects CO2Yield.And with following
Formula calculates conversion ratio：WhereinFor the amount (mol) of toluene parent material,For certain moment CO2Material amount (mol).
The multilayer TiO of table 12Nanotube based photocatalyst TN@SrTiO3@Ag@Bi2O3@Ag Activity evaluation
Claims (7)
- A kind of 1. multilayer TiO2Nanotube based photocatalyst, it is characterised in that：The photochemical catalyst is by TiO2Nanotube does base Bottom, it is sequentially depositing SrTiO3、Ag、Bi2O3, Ag composition, counted using the weight of catalyst as 100%, every layer of Ag mass fraction 0.5%, SrTiO3Mass fraction be 1%, Bi2O3Mass fraction be 1%, surplus TiO2Nanotube.
- 2. multilayer TiO described in claim 12The preparation method of nanotube based photocatalyst, comprises the following steps：（1）By TiO2Nanotube is put in the TiO that calcining is handled well in Muffle furnace2Nanotube；（2）By TiO2Nanotube is dissolved in ethanol, magnetic agitation；Take Sr (OH)2It is dissolved in pure water, ultrasound makes its uniform；Again will It is added drop-wise to TiO2In nanotube solution, magnetic agitation；Hydro-thermal afterwards, centrifuge washing are dried to obtain TN@SrTiO3；（3）By TN@SrTiO3It is dissolved in ethanol and water volume ratio 1:In 1 solution, magnetic agitation；Take AgNO3It is dissolved in ethanol and water body Product ratio 1:In 1 solution, ultrasound makes its uniform；TN@SrTiO are added dropwise to again3Magnetic agitation in solution；Microwave hydrothermal afterwards, Centrifuge washing is dried to obtain TN@SrTiO3@Ag；（4）By TN@SrTiO3@Ag are dissolved in ethanol, magnetic agitation；Take Bi (NO3)3It is dissolved in ethylene glycol and alcohol mixed solution, Ultrasound makes its uniform；TN@SrTiO are added dropwise to again3Magnetic agitation in@Ag solution；Microwave hydrothermal afterwards, centrifuge washing are dried, Calcine to obtain TN@SrTiO again3@Ag@Bi2O3；（5）According to step（3）Middle method is in TN@SrTiO3@Ag@Bi2O3Upper redeposited one layer of Ag obtains TN SrTiO3@Ag@ Bi2O3@Ag。
- 3. preparation method according to claim 2, it is characterised in that：Step（1）Described in calcination process, refer to 350 ~ 2 ~ 4 h are calcined under the conditions of 500 DEG C.
- 4. preparation method according to claim 2, it is characterised in that：Step（2）Described in the magnetic agitation time be 30 ~ 60 min, hydrothermal condition are 180 ~ 240 DEG C of h of hydro-thermal 18 ~ 30, and washing process refers to be washed several times with 0.05 ~ 0.2 M acetic acid, Washed several times with pure water and absolute ethyl alcohol again；Drying process refers to the h of freeze-day with constant temperature 6 ~ 24 in 60 ~ 80 DEG C of air atmosphere.
- 5. preparation method according to claim 2, it is characterised in that：Step（3）Described in the magnetic agitation time be 30 ~ 60 min, microwave hydrothermal parameter：Temperature is 120 ~ 180 DEG C, and the time is 1 ~ 3 h, and power is 300 ~ 500 W；Washing process refers to Washed several times with pure water and absolute ethyl alcohol；Drying process refers to the h of freeze-day with constant temperature 6 ~ 24 in 60 ~ 80 DEG C of air atmosphere.
- 6. preparation method according to claim 2, it is characterised in that：Step（4）Described in the magnetic agitation time be 30 ~ 60 min, microwave hydrothermal parameter：Temperature is 120 ~ 180 DEG C, and the time is 1 ~ 3 h, and power is 300 ~ 500 W；Washing process refers to Washed several times with pure water and absolute ethyl alcohol；Drying process refers to the h of freeze-day with constant temperature 6 ~ 24 in 60 ~ 80 DEG C of air atmosphere.Forge Burning process refers to 400 ~ 600 DEG C of 3 ~ 5 h of calcining in Muffle furnace.
- 7. the claim 1 ~ 6 multilayer TiO2Application of the nanotube based photocatalyst in as visible light catalyst.
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| CN108514886A (en) * | 2018-03-20 | 2018-09-11 | 中山大学 | A kind of argentum-based catalyzer for photo-thermal concerted catalysis degradation of toluene |
| CN109030594A (en) * | 2018-09-10 | 2018-12-18 | 合肥工业大学 | A kind of bismuthic acid Yin-silver-Nano tube array of titanium dioxide preparation method and applications |
| CN111139509A (en) * | 2020-01-10 | 2020-05-12 | 北京工业大学 | Preparation method of bismuth modified titanium dioxide nanotube array electrode |
| CN111595911A (en) * | 2020-06-24 | 2020-08-28 | 河北工业大学 | Preparation method of electrode group for detecting copper, iron and zinc ion mixed solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108514886A (en) * | 2018-03-20 | 2018-09-11 | 中山大学 | A kind of argentum-based catalyzer for photo-thermal concerted catalysis degradation of toluene |
| CN109030594A (en) * | 2018-09-10 | 2018-12-18 | 合肥工业大学 | A kind of bismuthic acid Yin-silver-Nano tube array of titanium dioxide preparation method and applications |
| CN111139509A (en) * | 2020-01-10 | 2020-05-12 | 北京工业大学 | Preparation method of bismuth modified titanium dioxide nanotube array electrode |
| CN111595911A (en) * | 2020-06-24 | 2020-08-28 | 河北工业大学 | Preparation method of electrode group for detecting copper, iron and zinc ion mixed solution |
| CN111595911B (en) * | 2020-06-24 | 2022-05-31 | 河北工业大学 | Preparation method of electrode group for detecting copper, iron and zinc ion mixed solution |
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