CN109046401A - 3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation and products thereof and application - Google Patents
3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation and products thereof and application Download PDFInfo
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- CN109046401A CN109046401A CN201810735009.5A CN201810735009A CN109046401A CN 109046401 A CN109046401 A CN 109046401A CN 201810735009 A CN201810735009 A CN 201810735009A CN 109046401 A CN109046401 A CN 109046401A
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- titanate esters
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 10
- 239000004332 silver Substances 0.000 title claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 title abstract description 32
- 230000003287 optical effect Effects 0.000 title abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 57
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 38
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims 3
- 239000010936 titanium Substances 0.000 claims 3
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000031700 light absorption Effects 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of 3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation method and products thereof and application, 3D pattern Ag/AgBr/TiO2Photochemical catalyst is with titanate esters, concentrated hydrochloric acid, CTAB, water, ethylene glycol, urea, silver nitrate, ammonium hydroxide is raw material, it is obtained by the method for loading silver under high temperature and high pressure environment, first titanate esters are mixed with concentrated hydrochloric acid, the aqueous solution of CTAB is added drop-wise in metatitanic acid ester solution again, a certain amount of ethylene glycol and urea are added separately in the mixed solution of above-mentioned titanate esters and CTAB, 150 DEG C of progress hydro-thermal reactions after mixing, silver nitrate and ammonium hydroxide are added in the suspension that hydro-thermal reaction obtains, centrifuge washing is dry after stirring for 24 hours, 2h is roasted at 400 DEG C, sample after roasting restores 3h under ultraviolet light.This method simple process, low for equipment requirements, the composite photo-catalyst of preparation has stronger response to quadracycline under visible light conditions.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide optical catalyst for being related to loading silver under high temperature and high pressure environment and
Its product and application more particularly to a kind of 3D pattern silver/silver bromide/titanium dioxide optical catalyst preparation and products thereof and are answered
With.
Background technique
Titanium dioxide is as a kind of wide bandgap semiconductor, due to its chemical property stabilization, efficient photocatalytic activity, extensively
For fields such as atmosphere, the degradation of water environment pollution object, antibacterial, deodorization and automatically cleanings.But the optical response range of titanium dioxide is purple
The area Wai Guang, it is low to the utilization rate of sunlight；And the electronics that excitation generates is easy to hole-recombination, photo-quantum efficiency is low, serious to restrict
Its in terms of practical application.In recent years, people attempt to pass through metal-doped, nonmetal doping, metal and Fei Jin
Belong to the means such as codope, semiconductors coupling and dye photoactivation, expand the optical response range of titanium dioxide, inhibits electronics and hole
It is compound, to improve the photocatalysis performance of titanium dioxide and its compound.Silver bromide is a kind of important inorganic light-sensitive material,
With very high visible light-responded, while silver bromide can form semiconductor heterostructure with titanium dioxide, inhibit electronics with
Hole-recombination improves the visible light catalysis activity of titanium dioxide.
Researcher has done certain research around the preparation of the composite material of titanium dioxide and silver bromide.Chinese patent
CN102874751A has invented a kind of AgBr/TiO using P25 as raw material2Preparation method.Chinese patent CN102909039A hair
A kind of core-shell structure Ag/AgBr/TiO is illustrated2Preparation method.But so far, compare table greatly for visible light photocatalytic degradation
Area 3D pattern Ag/AgBr/TiO2Preparation method have not been reported.
Summary of the invention
In view of the shortcomings of the prior art, it is an object of that present invention to provide a kind of 3D pattern silver/bromination silver/titanium dioxide (Ag/
AgBr/TiO2) photochemical catalyst preparation method.
Another object of the present invention is: providing a kind of 3D pattern Ag/AgBr/TiO that above-mentioned preparation method obtains2Light
Catalyst prod.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of 3D pattern Ag/AgBr/TiO2The preparation method of photochemical catalyst,
Using titanate esters, concentrated hydrochloric acid, CTAB, water, ethylene glycol, urea, silver nitrate, ammonium hydroxide as raw material, using the ultraviolet reduction of hydro-thermal-precipitating-
Technology combines, and is obtained by the method for loading silver under high temperature and high pressure environment, the specific steps are as follows:
1) first by titanate esters, example is that 1:50~200 mix in molar ratio with concentrated hydrochloric acid；
2) aqueous solution of cetyl trimethylammonium bromide (CTAB) is added drop-wise in above-mentioned metatitanic acid ester solution, by a certain amount of second
Two pure and mild urea are added separately in the mixed solution of above-mentioned titanate esters and CTAB, and the molar ratio of titanate esters and CTAB are 1:
0.5~1, the molar ratio of titanate esters and water is 1:1000~2000, is uniformly mixed；
3) hydro-thermal reaction is carried out in 150 DEG C of environment, silver nitrate and ammonium hydroxide, stirring is added in the suspension which obtains
Centrifuge washing is dry after for 24 hours；
4) 2h is roasted at 400 DEG C, the sample after roasting restores 3h under ultraviolet light, obtains 3D pattern Ag/AgBr/TiO2Light is urged
Agent.
The method of the present invention simple process, it is low for equipment requirements.
Wherein, the titanate esters are isopropyl titanate or butyl titanate.
The molar ratio of titanate esters and ethylene glycol is 1:1000~2000, the molar ratio of titanate esters and urea be 1:20~
40。
The molar ratio of titanate esters and silver nitrate is 1:0.05~0.3.
Hydro-thermal reaction under the conditions of 150 DEG C of temperature, the hydro-thermal reaction time be 8~for 24 hours.
The present invention is prepared with better simply technique, and product has 3D pattern, improves titanium dioxide specific surface area, widening it can
Light-exposed response range.
The present invention provides a kind of 3D pattern Ag/AgBr/TiO2Photochemical catalyst is the preparation side according to any of the above-described
What method obtained.
The present invention also provides a kind of 3D pattern Ag/AgBr/TiO2The application of photochemical catalyst, it is seen that under the conditions of light for pair
Quadracycline catalysis.
The preparation method of the titanium dioxide of 3D pattern load silver bromide of the present invention is specific as follows:
(1) titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred for uniformly first, titanate esters and salt
The molar ratio of acid is 1:50~200；
(2) cetyl trimethylammonium bromide (CTAB) is added in deionized water, is mixed and stirred for uniform CTAB aqueous solution；
(3) CTAB aqueous solution being added drop-wise in metatitanic acid ester solution and stirs 1h, the molar ratio of titanate esters and CTAB are 1:0.5~1,
The molar ratio of titanate esters and water is 1:1000~2000.
(4) a certain amount of ethylene glycol and urea are added separately in the mixed solution of above-mentioned titanate esters and CTAB, are stirred
Uniformly.The molar ratio of titanate esters and ethylene glycol is 1:1000~2000, and the molar ratio of titanate esters and urea is 1:20~40.
(5) above-mentioned mixed solution is added in 100mL water heating kettle, 150 DEG C of hydro-thermal reactions 8~generate 3D pattern for 24 hours
Titanium dioxide.
(6) silver nitrate and 2mL ammonium hydroxide are added in the suspension for the titanium dioxide of pattern containing 3D that hydro-thermal reaction obtains, are stirred
Mixing loads to silver bromide on 3D pattern titanium dioxide, centrifugation, and is washed respectively 3 times with ethyl alcohol and deionized water, at 80 DEG C
Lower dry 10h or more, wherein the molar ratio of titanate esters and silver nitrate is 1:0.05~0.3.
(7) sample of above-mentioned drying is roasted at 400 DEG C 2h, removes residual organic matter, obtained sample is in ultraviolet light
Lower reduction treatment 3h makes catalyst surface generate Ag0Nano particle obtains the Ag/AgBr/TiO of 3D pattern2。
It is combined using the ultraviolet reduction technique of hydro-thermal-precipitating-, composite material can make full use of the plasma of Ag nano particle
Resonance effects, the stronger visible light absorption capacity of AgBr semiconductor, TiO2The synergistic effects such as stronger photo-catalysis capability have excellent
The visible light catalysis activity of different degradation antibiotic.The composite photo-catalyst of preparation has quadracycline under visible light conditions
Relatively strong response.
The method of the present invention is simple, low for equipment requirements, which can increase the specific surface of titanium dioxide optical catalyst
Product widens the visible light-responded range of titanium dioxide optical catalyst.
Detailed description of the invention
Fig. 1 is 3D Ag/AgBr/TiO2Scanning electron microscope (SEM) photograph.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and operating process, but protection scope of the present invention is not limited to following embodiments.
The Ag/AgBr/TiO of 3D pattern2Performance evaluation carried out in quartz glass tube, evaluation object be 10mg/L reactive blue
Dye solution, photochemical catalyst dosage are 1mg/mL, and suspension stirs 1h.Suspension is exposed under xenon lamp, filtration ultraviolet light into
After row visible light photocatalytic degradation 180min, suspension is centrifuged 10min using 12000rpm as revolving speed.Utilize spectrophotometric determination
Reactive blue photocatalytic activity is calculated in reactive blue concentration in supernatant.
Embodiment 1
Firstly, isopropyl titanate or butyl titanate and concentrated hydrochloric acid are mixed and stirred for uniformly, the molar ratio of titanate esters and hydrochloric acid
Example is 1:50；Cetyl trimethylammonium bromide (CTAB) is added in deionized water, is mixed and stirred for uniformly.CTAB is water-soluble
Drop is added in metatitanic acid ester solution, stirs 1h.The molar ratio of titanate esters and CTAB are 1:0.5, the molar ratio of titanate esters and water
Example is 1:2000.A certain amount of ethylene glycol and urea are added separately in the mixed solution of above-mentioned titanate esters and CTAB, are stirred
Uniformly.The molar ratio of titanate esters and ethylene glycol is 1:1000, and the molar ratio of titanate esters and urea is 1:20.By above-mentioned mixing
Solution is added in 100mL water heating kettle, and 150 DEG C of hydro-thermal reactions generate the titanium dioxide of 3D pattern for 24 hours.By silver nitrate and 2mL ammonia
Water is added in the suspension for the titanium dioxide of pattern containing 3D that hydro-thermal reaction obtains, and stirring makes silver bromide load to 3D pattern for 24 hours
On titanium dioxide, centrifugation, and washed respectively 3 times with ethyl alcohol and deionized water, the dry 10h or more at 80 DEG C.Titanate esters and nitre
The molar ratio of sour silver is 1:0.05.The sample of above-mentioned drying is roasted into 2h at 400 DEG C, residual organic matter is removed, obtains
Sample reduction treatment 3h under ultraviolet light makes catalyst surface generate Ag0Nano particle obtains 3D Ag/AgBr/TiO2.Product
3D Ag/AgBr/TiO2Scanning electron microscope (SEM) photograph it is as shown in Figure 1.
By manufactured 3D Ag/AgBr/TiO2Photochemical catalyst carries out catalytic performance test with preceding experimental conditions, and measurement is lived
Property blue degradation rate be 55%.
Embodiment 2
Titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred for uniformly first, titanate esters and hydrochloric acid
Molar ratio is 1:100.Cetyl trimethylammonium bromide (CTAB) is added in deionized water, is mixed and stirred for uniformly.It will
CTAB aqueous solution is added drop-wise in metatitanic acid ester solution, stirs 1h.The molar ratio of titanate esters and CTAB are 1:1, titanate esters and water
Molar ratio is 1:1000.A certain amount of ethylene glycol and urea are added separately to above-mentioned titanate esters and the mixed solution of CTAB
In, it stirs evenly.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:20.It will
Above-mentioned mixed solution is added in 100mL water heating kettle, and 150 DEG C of hydro-thermal reactions generate the titanium dioxide of 3D pattern for 24 hours.By silver nitrate
It is added to 2mL ammonium hydroxide in the suspension for the titanium dioxide of pattern containing 3D that hydro-thermal reaction obtains, stirring loads to silver bromide for 24 hours
On 3D pattern titanium dioxide, centrifugation, and washed respectively 3 times with ethyl alcohol and deionized water, the dry 10h or more at 80 DEG C.Metatitanic acid
The molar ratio of ester and silver nitrate is 1:0.1.The sample of above-mentioned drying is roasted into 2h at 400 DEG C, residual organic matter is removed, obtains
The sample arrived reduction treatment 3h under ultraviolet light makes catalyst surface generate Ag0Nano particle obtains 3D Ag/AgBr/TiO2。
By manufactured 3D Ag/AgBr/TiO2Photochemical catalyst carries out catalytic performance test with preceding experimental conditions, and measurement is lived
Property blue degradation rate be 80.3%.
Embodiment 3
Titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred for uniformly first, titanate esters and hydrochloric acid
Molar ratio is 1:200.Cetyl trimethylammonium bromide (CTAB) is added in deionized water, is mixed and stirred for uniformly.It will
CTAB aqueous solution is added drop-wise in metatitanic acid ester solution, stirs 1h.The molar ratio of titanate esters and CTAB are 1:1, titanate esters and water
Molar ratio is 1:2000.A certain amount of ethylene glycol and urea are added separately to above-mentioned titanate esters and the mixed solution of CTAB
In, it stirs evenly.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:40.It will
Above-mentioned mixed solution is added in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 12h generate the titanium dioxide of 3D pattern.By silver nitrate
It is added to 2mL ammonium hydroxide in the suspension for the titanium dioxide of pattern containing 3D that hydro-thermal reaction obtains, stirring loads to silver bromide for 24 hours
On 3D pattern titanium dioxide, centrifugation, and washed respectively 3 times with ethyl alcohol and deionized water, the dry 10h or more at 80 DEG C.Metatitanic acid
The molar ratio of ester and silver nitrate is 1:0.3.The sample of above-mentioned drying is roasted into 2h at 400 DEG C, removes residual organic matter,
Obtained sample reduction treatment 3h under ultraviolet light makes catalyst surface generate Ag0Nano particle obtains 3D Ag/AgBr/
TiO2。
By manufactured 3D Ag/AgBr/TiO2Photochemical catalyst carries out catalytic performance test with preceding experimental conditions, and measurement is lived
Property blue degradation rate be 65.8%.
Embodiment 4
Titanate esters (isopropyl titanate or butyl titanate) and concentrated hydrochloric acid are mixed and stirred for uniformly first, titanate esters and hydrochloric acid
Molar ratio is 1:200.Cetyl trimethylammonium bromide (CTAB) is added in deionized water, is mixed and stirred for uniformly.It will
CTAB aqueous solution is added drop-wise in metatitanic acid ester solution, stirs 1h.The molar ratio of titanate esters and CTAB are 1:1, titanate esters and water
Molar ratio is 1:2000.A certain amount of ethylene glycol and urea are added separately to above-mentioned titanate esters and the mixed solution of CTAB
In, it stirs evenly.The molar ratio of titanate esters and ethylene glycol is 1:2000, and the molar ratio of titanate esters and urea is 1:30.It will
Above-mentioned mixed solution is added in 100mL water heating kettle, and 150 DEG C of hydro-thermal reaction 8h generate the titanium dioxide of 3D pattern.By silver nitrate
It is added to 2mL ammonium hydroxide in the suspension for the titanium dioxide of pattern containing 3D that hydro-thermal reaction obtains, stirring loads to silver bromide for 24 hours
On 3D pattern titanium dioxide, centrifugation, and washed respectively 3 times with ethyl alcohol and deionized water, the dry 10h or more at 80 DEG C.Metatitanic acid
The molar ratio of ester and silver nitrate is 1:0.1.The sample of above-mentioned drying is roasted into 2h at 400 DEG C, removes residual organic matter,
Obtained sample reduction treatment 3h under ultraviolet light makes catalyst surface generate Ag0Nano particle obtains 3D Ag/AgBr/
TiO2。
By manufactured 3D Ag/AgBr/TiO2Photochemical catalyst carries out catalytic performance test with preceding experimental conditions, and measurement is lived
Property blue degradation rate be 74.3%.
Claims (8)
1. a kind of 3D pattern Ag/AgBr/TiO2The preparation method of photochemical catalyst, which is characterized in that with titanate esters, concentrated hydrochloric acid,
CTAB, water, ethylene glycol, urea, silver nitrate, ammonium hydroxide are raw material, are obtained by the method for loading silver under high temperature and high pressure environment, specifically
Steps are as follows:
1) first by titanate esters, example is that 1:50~200 mix in molar ratio with concentrated hydrochloric acid；
2) aqueous solution of CTAB is added drop-wise in above-mentioned metatitanic acid ester solution, a certain amount of ethylene glycol and urea is added separately to
In the mixed solution for stating titanate esters and CTAB, the molar ratio of titanate esters and CTAB are 1:0.5~1, mole of titanate esters and water
Ratio is 1:1000~2000, is uniformly mixed；
3) hydro-thermal reaction is carried out in 150 DEG C of environment, silver nitrate and ammonium hydroxide, stirring is added in the suspension which obtains
Centrifuge washing is dry after for 24 hours；
4) 2h is roasted at 400 DEG C, the sample after roasting restores 3h under ultraviolet light, obtains 3D pattern Ag/AgBr/TiO2Photocatalysis
Agent.
2. 3D pattern Ag/AgBr/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that described
Titanate esters are isopropyl titanate or butyl titanate.
3. 3D pattern Ag/AgBr/TiO according to claim 1 or claim 22The preparation method of photochemical catalyst, which is characterized in that titanium
The molar ratio of acid esters and ethylene glycol is 1:1000~2000.
4. 3D pattern Ag/AgBr/TiO according to claim 1 or claim 22The preparation method of photochemical catalyst, which is characterized in that titanium
The molar ratio of acid esters and urea is 1:20~40.
5. 3D pattern Ag/AgBr/TiO according to claim 1 or claim 22The preparation method of photochemical catalyst, which is characterized in that titanium
The molar ratio of acid esters and silver nitrate is 1:0.05~0.3.
6. 3D pattern Ag/AgBr/TiO according to claim 12The preparation method of photochemical catalyst, which is characterized in that hydro-thermal is anti-
The time answered be 8~for 24 hours.
7. a kind of 3D pattern Ag/AgBr/TiO2Photochemical catalyst, any one of -6 preparation methods obtain according to claim 1.
8. a kind of 3D pattern Ag/AgBr/TiO according to claim 72The application of photochemical catalyst, it is seen that be used under the conditions of light
Quadracycline is catalyzed.
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