CN108311132A - A kind of preparation method of visible light ternary photochemical catalyst - Google Patents
A kind of preparation method of visible light ternary photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000013019 agitation Methods 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 11
- GNZPRLWDGQHPPE-UHFFFAOYSA-N hydroxysilane titanium Chemical compound [Ti].O[SiH3] GNZPRLWDGQHPPE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 48
- 239000004408 titanium dioxide Substances 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 titanium dioxide compound Chemical class 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000003466 welding 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to photocatalysis technology fields, and in particular to step 1 a kind of preparation method of visible light ternary photochemical catalyst tetrabutyl titanate is added into absolute ethyl alcohol, 30 60min are stirred by ultrasonic, obtain metatitanic acid alcohol liquid；Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains titanium silicon mixed alcohol liquid to being completely dissolved；Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium silicon dispersion liquid；Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 4 6h, obtains ternary mixed liquor；Step 5, ternary mixed liquor is put into 60 90min of vacuum distillation reaction in vacuum distillation reaction kettle, obtains viscous fluid；Step 6, viscous fluid is put into baking oven and dries 30 50min, then 20 40min of heat-agglomerating, obtain ternary photochemical catalyst.The present invention solves the problems, such as that the catalyst of graphene titanium dioxide performance in visible light region is bad, and the photochemical catalyst stability of preparation, the disposal efficiency are high.
Description
Technical field
The invention belongs to photocatalysis technology fields, and in particular to a kind of preparation method of visible light ternary photochemical catalyst.
Background technology
With the rapid development of science and technology, the living standard of the mankind is gradually rising.China is in terms of economic growth
Significant progress is achieved, productivity is greatly improved.But many areas in China be using welding as cost from
And so that economy is significantly promoted, therefore it may be seen that the small square built everywhere, to river in have discharged a large amount of industry dirty
Water, pm2.5 indexes only increase, our living environment causes anxiety.Water is Source of life, and water pollution is at the public affairs of the whole mankind
Enemy, how reducing the influence that water pollution is brought, to be us will consider the problems of.Now in terms of sewage disposal, there is absorption, manually
Salvage etc., to sum up, very single.And absorption method often causes secondary pollution, loses more than gain, in addition at many sewage
It is high to manage technical costs, is not easy to promote the use of.
Photocatalysis presents its good advantage as a kind of new technology.Compared to common sewage disposal technology, light is urged
Changing has lot of advantages, and first, reaction condition is mild, and degradable organic pollutant effect is good.；Secondly, of low cost, prepare letter
It is single, it is easy to operate；Furthermore it can be recycled, and photocatalysis Decomposition product is the pollution-free substances such as H2O ﹑ CO2 ﹑ N2, not will produce
Secondary pollution.Therefore, with very high economic value and social benefit.
Titanium dioxide has very excellent chemical property, such as chemical stability, electrical conductivity.Just because of it has very much
Advantage, so being applied to many fields.There are three types of type, rutile-type, Detitanium-ore-type, brookite types for titanium dioxide.Wherein,
Anatase titanium dioxide stability is good, and oxygen uptake ability is high, therefore is more widely applied.Anatase titanium dioxide has fine
Photo-catalysis capability, therefore photocatalyst for degrading pollutant can be made.Anatase titanium dioxide is full of electronics by one
Low-energy zone is formed with an empty high energy band, and low-energy zone and high energy band are separated by forbidden band, are wide bandgap semiconductor, when TiO2 by
To after the photon irradiation more than or equal to energy gap energy, electronics is stimulated from valence band jump to conduction band, can be generated in valence band
Hole, and hole has strong oxidizing property with light induced electron, it can be with degradable organic pollutant.But since titanium dioxide can only absorb purple
Outer light, and UV energy accounting in solar energy is extremely low, therefore titanium dioxide is unable to fully utilize sunlight；In addition photoproduction
The recombination rate of electrons and holes is much larger than its rate having an effect with organic matter, because of the two disadvantages so that titanium dioxide
Titanium photocatalysis performance is had a greatly reduced quality.
In order to solve the disadvantage that titanium dioxide, consider to introduce graphene particles.Graphene is one kind by single layer of carbon atom group
At bi-dimensional cellular shape lattice structure carbonaceous material, there is good electric conductivity, and specific surface area is very big.By itself and titanium dioxide
Titanium nanometer rods are compound, can substantially improve that titanium dioxide absorptivity is low, light induced electron and the easily compound disadvantage in hole.Its reason
As follows, graphene has certain adsorption capacity, and pollutant can be adsorbed onto to the surface of catalyst, accelerates reaction rate, separately
The satisfactory electrical conductivity of outer graphene can delay the compound of electron hole, and the bonding of graphene and titanium dioxide reduces can be very poor,
Catalyst is set to improve the utilization rate of sunlight.
The Chinese invention patent of Publication No. CN107308929A discloses a kind of graphene-nanometer titanium dioxide compound
The preparation method of photochemical catalyst, with graphite powder, the concentrated sulfuric acid, titanium trichloride, n-hexane, n-amyl alcohol, cetyl trimethyl bromination
Ammonium is raw material, is reacted by hydro-thermal method and graphene-nanometer titanium dioxide compound photochemical catalyst is made.This method is prepared compound
Photochemical catalyst has excellent photocatalysis performance, and the ability of degradable organic pollutant is strong, and can follow bad utilization, originally urges in addition
Agent also has the characteristic of absorption.But photochemical catalyst prepared by this method is with good performance in ultraviolet light range, can
Performance in light-exposed region is bad, cannot be satisfied the demand in market.
Invention content
For the problems of the prior art, the present invention provides a kind of preparation method of visible light ternary photochemical catalyst, solves
The catalyst of graphene-titanium dioxide bad problem of performance, the photochemical catalyst stability of preparation, light in visible light region
Degradation efficiency is high.
To realize the above technical purpose, the technical scheme is that：
A kind of preparation method of visible light ternary photochemical catalyst, the preparation method include the following steps：
Step 1, tetrabutyl titanate is added into absolute ethyl alcohol, 30-60min is stirred by ultrasonic, obtain metatitanic acid alcohol liquid；
Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains the mixing of titanium silicon to being completely dissolved
Alcohol liquid；
Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium
Silicon dispersion liquid；
Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 4-6h, obtains ternary mixed liquor；
Step 5, ternary mixed liquor is put into vacuum distillation reaction 60-90min in vacuum distillation reaction kettle, obtained sticky
Liquid；
Step 6, viscous fluid is put into baking oven and dries 30-50min, then heat-agglomerating 20-40min, obtain ternary light
Catalyst.
A concentration of 20-40g/L of the tetrabutyl titanate in absolute ethyl alcohol in the step 1, the ultrasonic agitation surpass
Acoustic frequency is 20-40kHz, and temperature is 30-60 DEG C.
The addition of silester in the step 2 is the 50-70% of tetrabutyl titanate quality, described to be slowly added dropwise
Rate of addition is 3-6mL/min, and the churned mechanically mixing speed is 2000-4000r/min.
Dispersant in the step 3 uses polyvinylpyrrolidone, and the addition of the dispersant is tetrabutyl titanate
1.2-1.3 times of quality.
The mass concentration of dispersant in deionized water in the step 3 is 0.3-0.9g/mL, and the dispersion liquid delays
The slow speed that is added is 5-15mL/min.
Graphene addition in the step 4 is 2.1-2.5 times of tetrabutyl titanate quality.
The supersonic frequency section of circulating ultrasonic reaction in the step 4 is 2.5-6.5kHz, temperature range 70-80
DEG C, the single program of the circulating ultrasonic reaction cycle is as follows：
| Supersonic frequency | Temperature | Time |
| 2.5kHz | 70℃ | 5-10min |
| 2.5-6.5kHz | 70-80℃ | 10-20min |
| 6.5kHz | 80℃ | 5-10min |
| 6.5-2.5kHz | 80-70℃ | 10-20min |
| 2.5kHz | 70℃ | 5-10min |
The pressure of vacuum distillation reaction in the step 5 is the 60-70% of atmospheric pressure, and temperature is 50-70 DEG C.
Drying temperature in the step 6 is 70-90 DEG C, and the temperature of the heat-agglomerating is 400-500 DEG C.
From the above, it can be seen that the present invention has following advantages：
1. the present invention solves the problems, such as that the catalyst of graphene-titanium dioxide performance in visible light region is bad, system
Standby photochemical catalyst stability, the disposal efficiency are high.
2. the present invention is mixed using tetrabutyl titanate with silester, it is titania-doped to form good silicon, has
There is good visible photophase, while mixed effect between the two can be greatly promoted using liquid phase method, improves the equal of doping
Even property.
3. the present invention can not only have good dispersion effect using polyvinylpyrrolidone as dispersant, by metatitanic acid
N-butyl is dispersed to silester in absolute ethyl alcohol, and can be used as coating agent, and tetrabutyl titanate is converted to form dioxy
Change titanium and silester converts the Silica-coated to be formed, forms good particle diameter distribution.
4. the present invention uses solvent of the deionized water as dispersant, the preliminarily solubilised of dispersant can not only be played, it is excellent
The group of dispersant is first opened, and tetrabutyl titanate can be promoted to form titanium dioxide and titanium dioxide with silicate hydrolyzate
Silicon.
5. the present invention can be reached using circulating ultrasonic method by the circulation change of ethyl alcohol volume come varying cyclically material concentration
To the effect for being sufficiently mixed absorption, while the exclusive clutch of ultrasonic reaction can ensure its directly effect to graphene surface,
The key that can be promoted between graphene and titanium dioxide, silica connects effect, effective to promote photocatalysis performance and photocatalysis
Respond section.
6. the present invention is removed polyvinylpyrrolidone by the way of sintering, while converting titanium dioxide to anatase titanium dioxide
Titanium dioxide promotes photocatalysis performance.
Specific implementation mode
The present invention will be described in detail in conjunction with the embodiments, but does not do any restriction to the claim of the present invention.
Embodiment 1
A kind of preparation method of visible light ternary photochemical catalyst, the preparation method include the following steps：
Step 1, tetrabutyl titanate is added into absolute ethyl alcohol, 30min is stirred by ultrasonic, obtain metatitanic acid alcohol liquid；
Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains the mixing of titanium silicon to being completely dissolved
Alcohol liquid；
Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium
Silicon dispersion liquid；
Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 4h, obtains ternary mixed liquor；
Step 5, ternary mixed liquor is put into vacuum distillation reaction 60min in vacuum distillation reaction kettle, obtains viscous fluid；
Step 6, viscous fluid is put into baking oven and dries 30min, then heat-agglomerating 20min, obtain ternary photochemical catalyst.
A concentration of 20g/L of the tetrabutyl titanate in absolute ethyl alcohol in the step 1, the supersonic frequency of the ultrasonic agitation
Rate is 20kHz, and temperature is 30 DEG C.
The addition of silester in the step 2 is the 50% of tetrabutyl titanate quality, the drop being slowly added dropwise
Acceleration is 3mL/min, and the churned mechanically mixing speed is 2000r/min.
Dispersant in the step 3 uses polyvinylpyrrolidone, and the addition of the dispersant is tetrabutyl titanate
1.2 times of quality.
The mass concentration of dispersant in deionized water in the step 3 is 0.3g/mL, and the slow of the dispersion liquid adds
It is 5mL/min to enter speed.
Graphene addition in the step 4 is 2.1 times of tetrabutyl titanate quality.
The supersonic frequency section of circulating ultrasonic reaction in the step 4 is 2.5-6.5kHz, temperature range 70-80
DEG C, the single program of the circulating ultrasonic reaction cycle is as follows：
| Supersonic frequency | Temperature | Time |
| 2.5kHz | 70℃ | 5min |
| 2.5-6.5kHz | 70-80℃ | 10min |
| 6.5kHz | 80℃ | 5min |
| 6.5-2.5kHz | 80-70℃ | 10min |
| 2.5kHz | 70℃ | 5min |
The pressure of vacuum distillation reaction in the step 5 is the 60% of atmospheric pressure, and temperature is 50 DEG C.
Drying temperature in the step 6 is 70 DEG C, and the temperature of the heat-agglomerating is 400 DEG C.
Embodiment 2
A kind of preparation method of visible light ternary photochemical catalyst, the preparation method include the following steps：
Step 1, tetrabutyl titanate is added into absolute ethyl alcohol, 60min is stirred by ultrasonic, obtain metatitanic acid alcohol liquid；
Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains the mixing of titanium silicon to being completely dissolved
Alcohol liquid；
Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium
Silicon dispersion liquid；
Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 6h, obtains ternary mixed liquor；
Step 5, ternary mixed liquor is put into vacuum distillation reaction 90min in vacuum distillation reaction kettle, obtains viscous fluid；
Step 6, viscous fluid is put into baking oven and dries 50min, then heat-agglomerating 40min, obtain ternary photochemical catalyst.
A concentration of 40g/L of the tetrabutyl titanate in absolute ethyl alcohol in the step 1, the supersonic frequency of the ultrasonic agitation
Rate is 40kHz, and temperature is 60 DEG C.
The addition of silester in the step 2 is the 70% of tetrabutyl titanate quality, the drop being slowly added dropwise
Acceleration is 6mL/min, and the churned mechanically mixing speed is 4000r/min.
Dispersant in the step 3 uses polyvinylpyrrolidone, and the addition of the dispersant is tetrabutyl titanate
1.3 times of quality.
The mass concentration of dispersant in deionized water in the step 3 is 0.9g/mL, and the slow of the dispersion liquid adds
It is 15mL/min to enter speed.
Graphene addition in the step 4 is 2.5 times of tetrabutyl titanate quality.
The supersonic frequency section of circulating ultrasonic reaction in the step 4 is 2.5-6.5kHz, temperature range 70-80
DEG C, the single program of the circulating ultrasonic reaction cycle is as follows：
| Supersonic frequency | Temperature | Time |
| 2.5kHz | 70℃ | 10min |
| 2.5-6.5kHz | 70-80℃ | 20min |
| 6.5kHz | 80℃ | 10min |
| 6.5-2.5kHz | 80-70℃ | 20min |
| 2.5kHz | 70℃ | 10min |
The pressure of vacuum distillation reaction in the step 5 is the 70% of atmospheric pressure, and temperature is 70 DEG C.
Drying temperature in the step 6 is 90 DEG C, and the temperature of the heat-agglomerating is 500 DEG C.
Embodiment 3
A kind of preparation method of visible light ternary photochemical catalyst, the preparation method include the following steps：
Step 1, tetrabutyl titanate is added into absolute ethyl alcohol, 50min is stirred by ultrasonic, obtain metatitanic acid alcohol liquid；
Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains the mixing of titanium silicon to being completely dissolved
Alcohol liquid；
Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium
Silicon dispersion liquid；
Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 5h, obtains ternary mixed liquor；
Step 5, ternary mixed liquor is put into vacuum distillation reaction 80min in vacuum distillation reaction kettle, obtains viscous fluid；
Step 6, viscous fluid is put into baking oven and dries 30-50min, then heat-agglomerating 30min, obtain ternary photocatalysis
Agent.
A concentration of 30g/L of the tetrabutyl titanate in absolute ethyl alcohol in the step 1, the supersonic frequency of the ultrasonic agitation
Rate is 30kHz, and temperature is 45 DEG C.
The addition of silester in the step 2 is the 60% of tetrabutyl titanate quality, the drop being slowly added dropwise
Acceleration is 5mL/min, and the churned mechanically mixing speed is 3000r/min.
Dispersant in the step 3 uses polyvinylpyrrolidone, and the addition of the dispersant is tetrabutyl titanate
1.3 times of quality.
The mass concentration of dispersant in deionized water in the step 3 is 0.6g/mL, and the slow of the dispersion liquid adds
It is 10mL/min to enter speed.
Graphene addition in the step 4 is 2.3 times of tetrabutyl titanate quality.
The supersonic frequency section of circulating ultrasonic reaction in the step 4 is 2.5-6.5kHz, temperature range 70-80
DEG C, the single program of the circulating ultrasonic reaction cycle is as follows：
| Supersonic frequency | Temperature | Time |
| 2.5kHz | 70℃ | 8min |
| 2.5-6.5kHz | 70-80℃ | 12min |
| 6.5kHz | 80℃ | 6min |
| 6.5-2.5kHz | 80-70℃ | 12min |
| 2.5kHz | 70℃ | 8min |
The pressure of vacuum distillation reaction in the step 5 is the 65% of atmospheric pressure, and temperature is 60 DEG C.
Drying temperature in the step 6 is 80 DEG C, and the temperature of the heat-agglomerating is 450 DEG C.
Performance test
Comparative example uses graphene-titanium dioxide optical catalyst.
Test method tests national standard using photocatalysis performance.
In conclusion the present invention has the following advantages：
1. the present invention solves the problems, such as that the catalyst of graphene-titanium dioxide performance in visible light region is bad, system
Standby photochemical catalyst stability, the disposal efficiency are high.
2. the present invention is mixed using tetrabutyl titanate with silester, it is titania-doped to form good silicon, has
There is good visible photophase, while mixed effect between the two can be greatly promoted using liquid phase method, improves the equal of doping
Even property.
3. the present invention can not only have good dispersion effect using polyvinylpyrrolidone as dispersant, by metatitanic acid
N-butyl is dispersed to silester in absolute ethyl alcohol, and can be used as coating agent, and tetrabutyl titanate is converted to form dioxy
Change titanium and silester converts the Silica-coated to be formed, forms good particle diameter distribution.
4. the present invention uses solvent of the deionized water as dispersant, the preliminarily solubilised of dispersant can not only be played, it is excellent
The group of dispersant is first opened, and tetrabutyl titanate can be promoted to form titanium dioxide and titanium dioxide with silicate hydrolyzate
Silicon.
5. the present invention can be reached using circulating ultrasonic method by the circulation change of ethyl alcohol volume come varying cyclically material concentration
To the effect for being sufficiently mixed absorption, while the exclusive clutch of ultrasonic reaction can ensure its directly effect to graphene surface,
The key that can be promoted between graphene and titanium dioxide, silica connects effect, effective to promote photocatalysis performance and photocatalysis
Respond section.
6. the present invention is removed polyvinylpyrrolidone by the way of sintering, while converting titanium dioxide to anatase titanium dioxide
Titanium dioxide promotes photocatalysis performance.
It is understood that above with respect to the specific descriptions of the present invention, it is merely to illustrate the present invention and is not limited to this
Technical solution described in inventive embodiments.It will be understood by those of ordinary skill in the art that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technique effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (9)
1. a kind of preparation method of visible light ternary photochemical catalyst, it is characterised in that：The preparation method includes the following steps：
Step 1, tetrabutyl titanate is added into absolute ethyl alcohol, 30-60min is stirred by ultrasonic, obtain metatitanic acid alcohol liquid；
Step 2, silester is slowly added dropwise into metatitanic acid alcohol liquid, mechanical agitation obtains titanium silicon mixed alcohol liquid to being completely dissolved；
Step 3, it adds a dispersant to and forms dispersion liquid in deionized water, be then slowly added into titanium silanol liquid and obtain titanium silicon point
Dispersion liquid；
Step 4, graphene is put into titanium silicon dispersion liquid, circulating ultrasonic reacts 4-6h, obtains ternary mixed liquor；
Step 5, ternary mixed liquor is put into vacuum distillation reaction 60-90min in vacuum distillation reaction kettle, obtains viscous fluid；
Step 6, viscous fluid is put into baking oven and dries 30-50min, then heat-agglomerating 20-40min, obtain ternary photocatalysis
Agent.
2. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
The supersonic frequency of a concentration of 20-40g/L of the tetrabutyl titanate in absolute ethyl alcohol in 1, the ultrasonic agitation are 20-40kHz,
Temperature is 30-60 DEG C.
3. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
The addition of silester in 2 is the 50-70% of tetrabutyl titanate quality, and the rate of addition being slowly added dropwise is 3-6mL/
Min, the churned mechanically mixing speed are 2000-4000r/min.
4. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
Dispersant in 3 uses polyvinylpyrrolidone, and the addition of the dispersant is 1.2-1.3 times of tetrabutyl titanate quality.
5. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
The mass concentration of dispersant in deionized water in 3 is 0.3-0.9g/mL, and the speed that is slowly added to of the dispersion liquid is 5-
15mL/min。
6. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
Graphene addition in 4 is 2.1-2.5 times of tetrabutyl titanate quality.
7. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
The supersonic frequency section of circulating ultrasonic reaction in 4 is 2.5-6.5kHz, and temperature range is 70-80 DEG C, and the circulating ultrasonic is anti-
The single program that should be recycled is as follows：
。
8. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
The pressure of vacuum distillation reaction in 5 is the 60-70% of atmospheric pressure, and temperature is 50-70 DEG C.
9. a kind of preparation method of visible light ternary photochemical catalyst according to claim 1, it is characterised in that：The step
Drying temperature in 6 is 70-90 DEG C, and the temperature of the heat-agglomerating is 400-500 DEG C.
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Application publication date: 20180724 |