CN109433178A - A kind of carrier photochemical catalyst of titanium dioxide-graphene oxide and preparation method thereof - Google Patents
A kind of carrier photochemical catalyst of titanium dioxide-graphene oxide and preparation method thereof Download PDFInfo
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- CN109433178A CN109433178A CN201811230605.4A CN201811230605A CN109433178A CN 109433178 A CN109433178 A CN 109433178A CN 201811230605 A CN201811230605 A CN 201811230605A CN 109433178 A CN109433178 A CN 109433178A
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- graphene oxide
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- titanium dioxide
- photochemical catalyst
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010936 titanium Substances 0.000 title claims abstract description 65
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000000499 gel Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002023 wood Substances 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
-
- B01J35/39—
-
- B01J35/51—
Abstract
The embodiment of the invention provides carrier photochemical catalysts of a kind of titanium dioxide-graphene oxide and preparation method thereof, including carrier and are covered in titanium dioxide-graphene oxide composite material of carrier surface；The density of the carrier is less than water.Titanium dioxide-graphene oxide composite material is covered in carrier surface, is easily recycled catalyst by the carrier photochemical catalyst of titanium dioxide-graphene oxide provided in an embodiment of the present invention；By using titanium dioxide-graphene oxide carrier photochemical catalyst prepared by preparation method of the invention, the titanium dioxide-graphene oxide composite material is evenly distributed in carrier surface, thus catalytic performance with higher.
Description
Technical field
The present invention relates to photocatalysis technology fields, urge more particularly to a kind of carrier light of titanium dioxide-graphene oxide
Agent and preparation method thereof.
Background technique
With the development of industry, in the waste water that industrial production gives off containing a large amount of complicated components, concentration is higher, difficult biology
The substance of degradation brings harm to ecological environment and human health.In the numerous method for treating water emerged, photocatalysis skill
Art is mild with its reaction condition, directly can receive the favor of environmental protection industry (epi) practitioner using the features such as solar energy, becomes useless
The hot spot of water treatment technology.Titanium dioxide-graphene oxide composite material has catalytic performance as a kind of catalysis material
Well, the features such as pollution-free, is more and more paid attention to.However titanium dioxide-graphene oxide composite wood of prior art production
Material is mostly pulverulence, it is difficult to be recycled；And it is multiple to be fixed on titanium dioxide-graphene oxide on carrier using existing method
Condensation material is often unevenly distributed, easy to reunite, causes catalytic efficiency not high.
Summary of the invention
The carrier photochemical catalyst for being designed to provide a kind of titanium dioxide-graphene oxide of the embodiment of the present invention, with reality
The efficient of existing catalyst utilizes and recycling.Specific technical solution is as follows:
First aspect present invention provides a kind of carrier photochemical catalyst of titanium dioxide-graphene oxide, including carrier and
It is covered in titanium dioxide-graphene oxide composite material of carrier surface；The density of the carrier is less than water.
In some embodiments of first aspect present invention, it is hollow through the quartz of coarse processing that the carrier is selected from surface
At least one of ball, glass hollow ball, metal hollow ball, ceramic hollow ball.
Second aspect of the present invention provides titanium dioxide-graphene oxide carrier light described in first aspect present invention and urges
The preparation method of agent, comprising the following steps:
Step 1: by graphite oxide powder in pure water ultrasonic disperse, obtain graphene oxide suspension, the oxidation stone
In black alkene suspension, the mass concentration of graphene oxide is 0.5~1.0g/L；
Butyl titanate, glacial acetic acid, distilled water: being successively added to absolute ethanol by step 2, stirs 60~120 minutes,
It is then transferred in 40~50 DEG C of water-baths, continues stirring 60~80 minutes, obtain white gels；
Step 3: graphene oxide suspension obtained by step 1 is added in white gels obtained by step 2, the oxygen
The volume ratio of graphite alkene suspension and the white gels is 1:(5~20), it stirs 24~48 hours, obtains titanium dioxide-
Graphene oxide liquid mixture；
Step 4: by carrier impregnation in the mixed liquor obtained by step 3, dipping temperature is 60~80 DEG C, dip time 16~
32 hours；
Step 5: after the carrier drying after step 4 impregnation, in inert gas, 400~450 DEG C of roastings 4~8
Hour, titanium dioxide-graphene oxide carrier photochemical catalyst is obtained after cooling.
In some embodiments of second aspect of the present invention, the graphite oxide powder is prepared by Hummer method, tool
Steps are as follows for body:
(1) in ice-water bath, 1g graphite and 0.5g sodium nitrate are sequentially added into the 30mL concentrated sulfuric acid, after stirring 5 minutes,
6g potassium permanganate is added, continues to be stirred to react 2 hours；
(2) 50mL pure water is added, is warming up to 98 DEG C, and kept for 30 minutes；
(3) 5mL hydrogen peroxide is added and terminates reaction；
(4) it filters while hot, and cleans filtrate to neutrality with hydrochloric acid and pure water, 60 DEG C of gained filtrate drying are to get arriving
Graphite oxide powder.
In some embodiments of second aspect of the present invention, the ultrasonic disperse time is 2~4 hours.
In some embodiments of second aspect of the present invention, the butyl titanate, glacial acetic acid, distilled water, anhydrous second
The volume ratio of alcohol is (10~20): (2~4): (10~15): (30~50).
In some embodiments of second aspect of the present invention, the inert gas be selected from nitrogen, carbon dioxide, argon gas and
At least one of helium.
In some embodiments of second aspect of the present invention, the quartz that the carrier is selected from rough surface processing is hollow
At least one of ball, glass hollow ball, metal hollow ball, ceramic hollow ball.
The carrier photochemical catalyst of titanium dioxide-graphene oxide provided in an embodiment of the present invention, by titanium dioxide-oxidation
Graphene composite material is covered in carrier surface, is easily recycled catalyst；It is prepared by using preparation method of the invention
Titanium dioxide-graphene oxide carrier photochemical catalyst, the titanium dioxide-graphene oxide composite material is in carrier surface point
Cloth is uniform, thus catalytic performance with higher.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the microphoto of titanium dioxide-graphene oxide carrier photocatalyst surface prepared by embodiment 2；
Fig. 2 is the microphoto of titanium dioxide-graphene oxide carrier photocatalyst surface prepared by comparative example 1；
Fig. 3 is the microphoto of titanium dioxide-graphene oxide carrier photocatalyst surface prepared by comparative example 2.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
First aspect present invention provides a kind of carrier photochemical catalyst of titanium dioxide-graphene oxide, including carrier and
It is covered in titanium dioxide-graphene oxide composite material of carrier surface；The density of the carrier is less than water.
Herein, " density is less than water " of carrier refers to that the carrier can float on the water surface；Including using density to be less than water
Material preparation carrier；Also include that reasonable shape or structure is made in the material that density is greater than water, can float on
On the water surface.
In some embodiments of first aspect present invention, it is hollow through the quartz of coarse processing that the carrier is selected from surface
At least one of ball, glass hollow ball, metal hollow ball, ceramic hollow ball.
The rough surface processing refers to the method by physics or chemistry, and the surface of relative smooth is made to become coarse,
Paper, grinder buffing, or handled using acid-base solution, this is technological means commonly used in the art, those skilled in the art
Member can be according to the suitable method of type and size selection of material, and the present invention is it is not limited here.Illustratively, soda acid is utilized
Carrier surface is pre-processed, carrier is cleaned, so that original hole is cleaned up or carried using the corrosivity of soda acid
Body surface face forms hole, increases the specific surface area of carrier, so that titanium dioxide-graphene oxide composite material be made firmly to adhere to
In carrier surface.
In some embodiments of first aspect present invention, used carrier is made of inorganic material, to water body
It is pollution-free；In addition the form of hollow sphere is used, carrier material swims in water surface, conducive to the recycling of catalyst；Hollow sphere exists
It is cheap and easy to get on the market, and the effect of view exhibition can be processed into according to project demands.
In some embodiments of first aspect present invention, the diameter of hollow sphere is selected from 1-200mm.
Second aspect of the present invention provides titanium dioxide-graphene oxide carrier light described in first aspect present invention and urges
The preparation method of agent, comprising the following steps:
Step 1: by graphite oxide powder in pure water ultrasonic disperse, obtain graphene oxide suspension, the oxidation stone
In black alkene suspension, the mass concentration of graphene oxide is 0.5~1.0g/L；
Butyl titanate, glacial acetic acid, distilled water: being successively added in dehydrated alcohol by step 2, stirs 60~120 points
Clock is then transferred in 40~50 DEG C of water-baths, continues stirring 60~80 minutes, obtain white gels；
Step 3: graphene oxide suspension obtained by step 1 is added in white gels obtained by step 2, the oxygen
The volume ratio of graphite alkene suspension and the white gels is 1:(5~20), it stirs 24~48 hours, obtains titanium dioxide-
Graphene oxide liquid mixture；
Step 4: by carrier impregnation in the mixed liquor obtained by step 3, dipping temperature is 60~80 DEG C, dip time 16~
32 hours；
Step 5: after the carrier drying after step 4 impregnation, in inert gas, 400~450 DEG C of roastings 4~8
Hour, titanium dioxide-graphene oxide carrier photochemical catalyst is obtained after cooling.
In the present invention, temperature is not particularly illustrated under room temperature or at room temperature, i.e., relevant operation does not need especially to examine
Considering temperature influences, and does not need heating or refrigeration processing.
In some embodiments of second aspect of the present invention, the graphite oxide powder can be purchased from commercial sources,
It can be prepared by Hummer method, the specific steps are as follows:
(1) in ice-water bath, 1g graphite and 0.5g sodium nitrate are sequentially added in the 30mL concentrated sulfuric acid (mass fraction 98%),
Stirring after five minutes, is added 6g potassium permanganate, continues to be stirred to react 2 hours；It needs to control reaction temperature in the process and be no more than
35℃；
(2) 50mL pure water is added, is warming up to 98 DEG C, and kept for 30 minutes；
(3) 5mL hydrogen peroxide is added and terminates reaction；
(4) it filters while hot, and cleans filtrate to neutrality with hydrochloric acid and pure water, 60 DEG C of gained filtrate drying are to get arriving
Graphite oxide powder.
Hummer method of the present invention is that this field prepares the common method of graphene oxide, those skilled in the art
Appropriate adjustment can be carried out to reaction condition according to the actual situation, the present invention is it is not limited here.
In some embodiments of second aspect of the present invention, the ultrasonic disperse time is 2~4 hours in step 1, favorably
In the evenly dispersed of graphene oxide.
In some embodiments of second aspect of the present invention, the mixing speed in step 2 can be 200~300r/
min。
It is that graphene oxide suspension is direct that this field, which prepares titanium dioxide-graphene oxide liquid mixture common method,
It is mixed with butyl titanate, glacial acetic acid, dehydrated alcohol etc., a step generates titanium dioxide-graphene oxide liquid mixture；The method is raw
At titanium dioxide-graphene oxide liquid mixture in, titanium dioxide is easy agglomerate, therefore titanium dioxide is difficult to be uniformly distributed in stone
Black alkene surface；And in the present invention, inventor is it was unexpectedly observed that be first added to nothing for butyl titanate, glacial acetic acid, a small amount of distilled water
Water-ethanol is prepared into gel, and the addition of a small amount of distilled water makes butyl titanate that initial hydrolysis occur, generates a small amount of titanium dioxide,
Titanium dioxide can be made tentatively to obtain evenly dispersed, after subsequent addition graphene oxide, generated titanium dioxide can be
The rapid occupy-place of surface of graphene oxide reduces the absorption of other substances on the surface of graphene, improves the load factor of titanium dioxide,
Can also titanium dioxide be made to be more evenly distributed in surface of graphene oxide simultaneously.
In some embodiments of second aspect of the present invention, the butyl titanate, glacial acetic acid, distilled water, anhydrous second
The volume ratio of alcohol is (10~20): (2~4): (10~15): (30~50).
In step 4, by dipping, titanium dioxide and graphene oxide is made to be evenly affixed to carrier table by chemical deposition
Face.
In some embodiments of second aspect of the present invention, the drying in step 5 can dry in air dry oven
12-24 hours.
In some embodiments of second aspect of the present invention, the inert gas be selected from nitrogen, carbon dioxide, argon gas and
At least one of helium.
In some embodiments of second aspect of the present invention, it is hollow through the quartz of coarse processing that the carrier is selected from surface
At least one of ball, glass hollow ball, metal hollow ball, ceramic hollow ball.
Heretofore described pure water can be the common distilled water in laboratory or deionized water.
The preparation of 1 graphene oxide powder of embodiment
1, in ice-water bath, to equipped with the 30mL concentrated sulfuric acid (concentration 98%) conical flask in sequentially add 1g graphite and
After stirring 5min, 6g potassium permanganate is added in 0.5g sodium nitrate, continues to be stirred to react 2h, temperature is no more than 35 DEG C；
2,50mL pure water is added, is warming up to 98 DEG C, and keep 30min；
3,5mL hydrogen peroxide (30% concentration) is added and terminates reaction；Heat filtering, and filtrate is cleaned into hydrochloric acid and pure water
Property, 60 DEG C of gained filtrate drying are graphene oxide powder.
The preparation of titanium dioxide-graphene oxide carrier photochemical catalyst of the invention
Embodiment 2
1, the graphene oxide powder for preparing embodiment 1 ultrasonic disperse 4h in pure water obtains graphene oxide suspension
Liquid, wherein the mass concentration of graphene oxide is 1.0g/L；
2,50mL dehydrated alcohol successively at room temperature, is added in butyl titanate 20mL, glacial acetic acid 4mL, distilled water 15mL
In, it is transferred in 50 DEG C of water-baths after stirring 120min under the conditions of 200~300r/min of low whipping speed, continues to stir 80min
Obtain white gels；
3,10mL graphene oxide suspension is added in 100mL white gels, 48h is stirred under room temperature to get titanium dioxide
Titanium-graphene oxide liquid mixture；
4, the ceramic hollow ball that the diameter of rough surface processing is 100mm is impregnated in mixed liquor, dipping temperature 80
DEG C, dip time 32h；
5, it after lifting out the ceramic hollow ball after impregnation, is transferred in air dry oven and dries for 24 hours, in nitrogen protection
Under, 450 DEG C of roasting 8h obtain titanium dioxide-graphene oxide carrier photochemical catalyst after cooling.
Embodiment 3
Titanium dioxide-graphene oxide carrier photochemical catalyst is prepared according to the method for embodiment 2, it is different from embodiment 2
Place is: carrier uses diameter for the quartzy hollow sphere of 10mm.
Embodiment 4
Titanium dioxide-graphene oxide carrier photochemical catalyst is prepared according to the method for embodiment 2, it is different from embodiment 2
Place is: carrier uses diameter for the iron hollow sphere of 200mm.
Embodiment 5
Titanium dioxide-graphene oxide carrier photochemical catalyst is prepared according to the method for embodiment 2, it is different from embodiment 2
Place is: at room temperature, successively butyl titanate 10mL, glacial acetic acid 2mL, distilled water 10mL being added in 50mL dehydrated alcohol.
Embodiment 6
Titanium dioxide-graphene oxide carrier photochemical catalyst is prepared according to the method for embodiment 2, it is different from embodiment 2
Place is: at room temperature, successively butyl titanate 20mL, glacial acetic acid 4mL, distilled water 15mL being added in 30mL dehydrated alcohol.
The preparation of the carrier photochemical catalyst of another titanium dioxide-graphene oxide of comparative example 1
1, the graphene oxide powder for preparing embodiment 1 ultrasonic disperse 4h in pure water obtains graphene oxide suspension
Liquid, wherein the mass concentration of graphene oxide is 1.0g/L；
2,1g titania powder is added into 10mL graphene oxide suspension, 48h is stirred under room temperature to get titanium dioxide
Titanium-graphene oxide liquid mixture；
3, by the ceramic hollow ball dipping of rough surface processing with mixed liquor, dipping temperature is 80 DEG C, dip time
32h；
4, it after lifting out the ceramic hollow ball after impregnation, is transferred in air dry oven and dries for 24 hours, in nitrogen protection
Under, 450 DEG C of roasting 8h obtain titanium dioxide-graphene oxide carrier photochemical catalyst after cooling.
The preparation of the carrier photochemical catalyst of another titanium dioxide-graphene oxide of comparative example 2
1, the graphene oxide powder for preparing embodiment 1 ultrasonic disperse 4h in pure water obtains graphene oxide suspension
Liquid, wherein the mass concentration of graphene oxide is 1.0g/L；
2, successively slowly polyethylene glycol, glacial acetic acid and butyl titanate are added under the conditions of low whipping speed is 50r/min
Mixed liquor is made into dehydrated alcohol, mass concentration is successively are as follows: polyethylene glycol 2.5g/L, glacial acetic acid 0.3g/L, four fourth of metatitanic acid
Ester 0.lg/L；
3, the graphene oxide water slurry 2mL for taking step 1 to prepare is that 50 μ L/min are added drop-wise to step with rate of addition
It in the two 30mL mixed liquors prepared, is at the uniform velocity stirred at 15 DEG C 1 day, forms titanium dioxide-graphene oxide liquid mixture；
4, by the ceramic hollow ball dipping of rough surface processing with mixed liquor, dipping temperature is 80 DEG C, dip time
32h；
5, it after lifting out the ceramic hollow ball after impregnation, is transferred in air dry oven and dries for 24 hours, in nitrogen protection
Under, 450 DEG C of roasting 8h obtain titanium dioxide-graphene oxide carrier photochemical catalyst after cooling.
Titanium dioxide-graphene oxide carrier photocatalyst surface prepared by embodiment 2, comparative example 1 and comparative example 2
Micro- electron microscope analysis
Titanium dioxide-graphene oxide carrier photocatalyst surface prepared by embodiment 2, comparative example 1 and comparative example 2
Micro- electromicroscopic photograph difference it is as shown in Figure 1, Figure 2 and Figure 3, it can be seen that visible gully shape structure in Fig. 2, such as black in Fig. 2
Shown in the enclosed position of dotted line, illustrate that titanium dioxide-graphene oxide composite material prepared by comparative example 1 is main in carrier surface
In block structure, it can be understood as, one piece one piece of titanium dioxide-graphene oxide composite material intersperses among carrier surface,
Gully shape structure in middle Fig. 2 is the boundary of block structure；Almost without load upper two in the enclosed position of solid white line in Fig. 3
Titanium oxide-graphene oxide composite material, is shown carrier surface, it is possible thereby to illustrate, dioxy prepared by comparative example 2
Change in titanium-graphene oxide carrier photochemical catalyst, titanium dioxide-graphene oxide composite material is distributed simultaneously in carrier surface
Unevenly.And titanium dioxide-the graphene oxide composite material shown in Fig. 1 is continuously covered with carrier surface, both without piecemeal
The phenomenon that, also without unlapped situation, illustrate the titanium dioxide-graphene oxide carrier prepared using method of the invention
Photochemical catalyst, surface titanium dioxide-graphene oxide composite material is more evenly.
Taking with a collection of coal chemical industry reverse osmosis concentrated water is process object, and embodiment 2,1 and of comparative example are respectively put into waste water
Titanium dioxide-graphene oxide carrier photochemical catalyst prepared by comparative example 2, after the solar radiation of 4h, coal chemical industry is anti-
It is as shown in table 1 to permeate concentrated water pollutants removal rate:
Table 1
| COD removal rate/% | Percent of decolourization/% | |
| Embodiment 2 | 79.2 | 87.5 |
| Comparative example 1 | 70.1 | 60.2 |
| Comparative example 2 | 73.4 | 78.5 |
As can be seen from the results, under the same conditions, titanium dioxide-graphene oxide carrier photocatalysis of the invention
Agent will be substantially better than titanium dioxide-graphene oxide carrier of other methods preparation to the treatment effect of dirty water pollutant
Photochemical catalyst illustrates titanium dioxide-graphene oxide carrier photochemical catalyst catalytic performance with higher of the invention.
Above to a kind of carrier photochemical catalyst of titanium dioxide-graphene oxide provided by the present invention and preparation method thereof
It is described in detail.Principle and implementation of the present invention are described for specific embodiment used herein, above
The explanation of embodiment is merely used to help understand method and its central idea of the invention.It should be pointed out that for the general of this field
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for logical technical staff, this
A little improvement and modification also fall into the protection of the claims in the present invention.
Claims (8)
1. a kind of carrier photochemical catalyst of titanium dioxide-graphene oxide, which is characterized in that including carrier and be covered in carrier table
Titanium dioxide-the graphene oxide composite material in face；The density of the carrier is less than water.
2. the carrier photochemical catalyst of titanium dioxide-graphene oxide as described in claim 1, which is characterized in that the carrier
At least one of quartzy hollow sphere, glass hollow ball, metal hollow ball, ceramic hollow ball selected from surface through coarse processing.
3. the preparation method of the carrier photochemical catalyst of titanium dioxide-graphene oxide described in claim 1, which is characterized in that
The following steps are included:
Step 1: by graphite oxide powder in pure water ultrasonic disperse, obtain graphene oxide suspension, the graphene oxide
In suspension, the mass concentration of graphene oxide is 0.5~1.0g/L；
Butyl titanate, glacial acetic acid, distilled water: being successively added in dehydrated alcohol by step 2, stirring 60~120 minutes, so
After be transferred in 40~50 DEG C of water-baths, continue stirring 60~80 minutes, obtain white gels；
Step 3: graphene oxide suspension obtained by step 1 is added in white gels obtained by step 2, the oxidation stone
The volume ratio of black alkene suspension and the white gels is 1:(5~20), it stirs 24~48 hours, obtains titanium dioxide-oxidation
Graphene mixed liquor；
Step 4: by carrier impregnation in the mixed liquor obtained by step 3, dipping temperature is 60~80 DEG C, and dip time 16~32 is small
When；
Step 5: after the carrier drying after step 4 impregnation, in inert gas, 400~450 DEG C of roastings 4~8 are small
When, titanium dioxide-graphene oxide carrier photochemical catalyst is obtained after cooling.
4. according to the method described in claim 3, having it is characterized in that, the graphite oxide powder is prepared by Hummer method
Steps are as follows for body:
(1) in ice-water bath, 1g graphite and 0.5g sodium nitrate are sequentially added into the 30mL concentrated sulfuric acid, after five minutes, 6g is added in stirring
Potassium permanganate continues to be stirred to react 2 hours；
(2) 50mL pure water is added, is warming up to 98 DEG C, and kept for 30 minutes；
(3) 5mL hydrogen peroxide is added and terminates reaction；
(4) it filters while hot, and cleans filtrate to neutrality with hydrochloric acid and pure water, 60 DEG C of gained filtrate dry to get oxidation is arrived
Powdered graphite.
5. according to the method described in claim 3, it is characterized in that, the ultrasonic disperse time is 2~4 hours.
6. according to the method described in claim 3, it is characterized in that, the butyl titanate, glacial acetic acid, distilled water, anhydrous second
The volume ratio of alcohol is (10~20): (2~4): (10~15): (30~50).
7. according to the method described in claim 3, it is characterized in that, the inert gas be selected from nitrogen, carbon dioxide, argon gas and
At least one of helium.
8. according to the method described in claim 3, it is characterized in that, the carrier is selected from the quartzy hollow of rough surface processing
At least one of ball, glass hollow ball, metal hollow ball, ceramic hollow ball.
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