CN106964378A - A kind of preparation method of fluorinated graphene composite visible light response catalyst - Google Patents
A kind of preparation method of fluorinated graphene composite visible light response catalyst Download PDFInfo
- Publication number
- CN106964378A CN106964378A CN201710101141.6A CN201710101141A CN106964378A CN 106964378 A CN106964378 A CN 106964378A CN 201710101141 A CN201710101141 A CN 201710101141A CN 106964378 A CN106964378 A CN 106964378A
- Authority
- CN
- China
- Prior art keywords
- preparation
- visible light
- znbi
- compound
- light response
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000004298 light response Effects 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 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 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- -1 Graphite Alkene Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide 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
- 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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of new fluorinated graphene composite visible light response catalyst, fluorinated graphene is made in graphene oxide by it after hydro-thermal reaction（FG）, FG and bismuth nitrate, zinc nitrate are then generated into FG ZnBi through solvent thermal reaction2O4Compound, then by gained FG ZnBi2O4TiO is made with butyl titanate reaction in compound2‑FG‑ZnBi2O4Compound, produces the fluorinated graphene composite visible light response catalyst.Gained catalyst under the conditions of visible light-responded to environment in the degraded of organic pollution show good catalytic activity and stability, it is reusable, it is environmentally friendly.
Description
Technical field
The invention belongs to catalysis material preparation field, and in particular to a kind of fluorinated graphene composite visible light response catalysis
The preparation method of agent.
Background technology
Photocatalysis technology can remove environmental contaminants by the method for high-efficiency environment friendly, and its principle is in light using photochemical catalyst
Excited according under generation electronics and hole by debirs oxidation Decomposition.Therefore, photocatalysis technology is considered as a kind of energy-saving ring
The environmental improvement technology protect, having a extensive future.Titanium dioxide in conventional photochemical catalyst（TiO2）Performance it is more excellent, be
Most studied one kind.But TiO2Greater band gap, to the utilization ratio of solar energy than relatively low, the ability only under ultraviolet light
Its excellent performance is given play to.Although researchers attempt to be modified it by various methods, all can not be fundamentally
Solve the problem of its is visible light-responded poor.Therefore, catalysis material of the exploitation with good visible light-responded performance gradually by
Pay attention to, one of development trend as photocatalysis research field.
Recent study finds that the photocatalytic activity of photochemical catalyst can be effectively improved by building artificial Z-type photocatalytic system.Z
Type photocatalytic system has the advantages that protrusion：(1) by two-photon excitation process, it is respectively completed on different photochemical catalysts also
Original reaction and oxidation reaction；(2) photochemical catalyst in Z-type photocatalytic system need to only meet respective photoexcitation process respectively and right
The half-reaction answered, reduces the thermodynamic requirement of light-catalyzed reaction, and the selection and design for catalysis material provide very big sky
Between；(3) oxidation reaction and reduction reaction process are separated from each other, and effectively suppress the generation of back reaction；(4) electronic media, Z-type are utilized
Light induced electron in photocatalytic system can be efficiently separated and transmitted with hole, keep stronger redox ability；(5) hydrogen is produced
The photohole of catalyst is mutually combined with the light induced electron in production VPO catalysts, enhances the stability of photocatalytic system.Graphite
Alkene is with sp by carbon atom2The hexagon of hybridized orbit composition is in the flat film of honeycomb lattice, can be fast for Z-type photocatalytic system
Speed transmission electronics, but this structure also causes the unstability of graphene, it is former by increasing fluorine around the carbon atom of graphene
Son, makes graphene partially fluorinated or all fluorinations, has both maintained the performance of graphene high intensity, and because the introducing band of fluorine atom
Come surface and can reduce, the interface that hydrophobicity enhancing and Bandgap extension etc. are novel and physical and chemical performance, be mechanical performance, chemistry
The compound of stability and excellent thermal stability, is described as " two-dimentional Teflon ".
Based on this, the present invention designs, is prepared for a kind of new fluorinated graphene composite visible light response catalyst, the catalysis
Agent degraded environmental organic pollutant is very capable, and the technology is not only for the system for designing and improving visible light responsive photocatalyst
Preferable directive significance is had, is also with good business for the popularization of visible light response catalyst from now in actual applications
Industry is worth.
The content of the invention
It is an object of the invention to provide a kind of preparation method of fluorinated graphene composite visible light response catalyst, its institute
Catalyst under the conditions of visible light-responded to environment in the degraded of organic pollution show good catalytic activity and stably
Property, it is reusable, it is environmentally friendly.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of fluorinated graphene composite visible light response catalyst, it comprises the following steps：
Step 1: FG preparation：
1）By 1g graphene oxides in 1L deionized waters ultrasonic disperse 30-60min, obtain graphene oxide dispersion；
2）Gained graphene oxide dispersion is added in the water heating kettle with polytetrafluoroethyllining lining, 0.01- is then added
0.05g sodium fluorides, water heating kettle, which is tightened, makes its closed, the insulation reaction 3-12h at 180 DEG C；
3）After question response terminates, it is allowed to naturally cool to room temperature, then by reacting liquid filtering, filter cake is repeatedly washed with ultra-pure water,
Until cleaning solution pH value reaches neutrality, then gained solid product is dried, FG is obtained；
Step 2: FG-ZnBi2O4The preparation of compound：
1）Absolute ethyl alcohol is added to be configured to mixed solution bismuth nitrate 0.1-0.5g and zinc nitrate 0.3-0.8g；
2）By gained FG 1g ultrasonic disperse 30-60min in absolute ethyl alcohol, then add and prepared under the conditions of magnetic agitation
Mixed solution, continue stir 30 min after, be transferred into polytetrafluoroethylliner liner, load stainless steel cauldron, 180 DEG C
Lower insulation reaction 3-12h；
3）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain FG-ZnBi2O4Compound；
Step 3: TiO2-FG-ZnBi2O4The preparation of compound：
1）By gained FG-ZnBi2O4Compound 1g ultrasonic disperse 30-60min in absolute ethyl alcohol, then in magnetic agitation condition
Lower addition 0.5g butyl titanates, continue to stir after 30 min, mixed liquor are transferred in polytetrafluoroethylliner liner, load stainless
Steel reactor, insulation reaction 3-12 h at 180 DEG C；
2）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain TiO2-FG-ZnBi2O4Compound, as described fluorinated graphene is combined visible
Photoresponse catalyst.
The remarkable advantage of the present invention is：The present invention is with fluorinated graphene（FG）It is used as the fid of Z-type photocatalytic system
Material, ZnBi2O4With TiO2Collectively as the catalytic active component of Z-type photocatalytic system, the high electronics of fluorinated graphene is made full use of
Mobility effect, is provided one " express passway ", so that greatly for semiconductor interface by the transmission of the photo-generated carrier produced after illumination
It is big to improve TiO2Photocatalyst activity.Under the conditions of visible light-responded, gained composite visible light response catalyst is in environment
The degraded of organic pollution shows good catalytic activity and stability, reusable, environmentally friendly.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
First, FG preparation：
1）By 1g graphene oxides in 1L deionized waters ultrasonic disperse 30min, obtain graphene oxide dispersion；
2）Gained graphene oxide dispersion is added in the water heating kettle with polytetrafluoroethyllining lining, 0.01g is then added
Sodium fluoride, water heating kettle, which is tightened, makes its closed, the insulation reaction 3h at 180 DEG C；
3）After question response terminates, it is allowed to naturally cool to room temperature, then by reacting liquid filtering, filter cake is repeatedly washed with ultra-pure water,
Until cleaning solution pH value reaches neutrality, then gained solid product is dried, FG is obtained；
2nd, FG-ZnBi2O4The preparation of compound：
1）Absolute ethyl alcohol is added to be configured to mixed solution bismuth nitrate 0.1g and zinc nitrate 0.3g；
2）By gained FG 1g ultrasonic disperse 30min in absolute ethyl alcohol, prepared mixed is then added under the conditions of magnetic agitation
Solution is closed, continues to stir after 30 min, is transferred into polytetrafluoroethylliner liner, loads at stainless steel cauldron, 180 DEG C and protects
Temperature reaction 3h；
3）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain FG-ZnBi2O4Compound；
3rd, TiO2-FG-ZnBi2O4The preparation of compound：
1）By gained FG-ZnBi2O4Compound 1g ultrasonic disperse 30min in absolute ethyl alcohol, then under the conditions of magnetic agitation
Butyl titanate 0.5g is added, continues to stir after 30 min, mixed liquor is transferred in polytetrafluoroethylliner liner, load stainless steel
Reactor, the h of insulation reaction 3 at 180 DEG C；
2）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain TiO2-FG-ZnBi2O4Compound.
Embodiment 2
First, FG preparation：
1）By 1g graphene oxides in 1L deionized waters ultrasonic disperse 40min, obtain graphene oxide dispersion；
2）Gained graphene oxide dispersion is added in the water heating kettle with polytetrafluoroethyllining lining, 0.03g is then added
Sodium fluoride, water heating kettle, which is tightened, makes its closed, the insulation reaction 6h at 180 DEG C；
3）After question response terminates, it is allowed to naturally cool to room temperature, then by reacting liquid filtering, filter cake is repeatedly washed with ultra-pure water,
Until cleaning solution pH value reaches neutrality, then gained solid product is dried, FG is obtained；
2nd, FG-ZnBi2O4The preparation of compound：
1）Absolute ethyl alcohol is added to be configured to mixed solution bismuth nitrate 0.2g and zinc nitrate 0.5g；
2）By gained FG 1g ultrasonic disperse 40min in absolute ethyl alcohol, prepared mixed is then added under the conditions of magnetic agitation
Solution is closed, continues to stir after 30 min, is transferred into polytetrafluoroethylliner liner, loads at stainless steel cauldron, 180 DEG C and protects
Temperature reaction 6h；
3）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain FG-ZnBi2O4Compound；
3rd, TiO2-FG-ZnBi2O4The preparation of compound：
1）By gained FG-ZnBi2O4Compound 1g ultrasonic disperse 40min in absolute ethyl alcohol, then under the conditions of magnetic agitation
Butyl titanate 0.5g is added, continues to stir after 30 min, mixed liquor is transferred in polytetrafluoroethylliner liner, load stainless steel
Reactor, the h of insulation reaction 6 at 180 DEG C；
2）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain TiO2-FG-ZnBi2O4Compound.
Embodiment 3
First, FG preparation：
1）By 1g graphene oxides in 1L deionized waters ultrasonic disperse 60min, obtain graphene oxide dispersion；
2）Gained graphene oxide dispersion is added in the water heating kettle with polytetrafluoroethyllining lining, 0.05g is then added
Sodium fluoride, water heating kettle, which is tightened, makes its closed, the insulation reaction 12h at 180 DEG C；
3）After question response terminates, it is allowed to naturally cool to room temperature, then by reacting liquid filtering, filter cake is repeatedly washed with ultra-pure water,
Until cleaning solution pH value reaches neutrality, then gained solid product is dried, FG is obtained；
2nd, FG-ZnBi2O4The preparation of compound：
1）Absolute ethyl alcohol is added to be configured to mixed solution bismuth nitrate 0.5g and zinc nitrate 0.8g；
2）By gained FG 1g ultrasonic disperse 60min in absolute ethyl alcohol, prepared mixed is then added under the conditions of magnetic agitation
Solution is closed, continues to stir after 30 min, is transferred into polytetrafluoroethylliner liner, loads at stainless steel cauldron, 180 DEG C and protects
Temperature reaction 12h；
3）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain FG-ZnBi2O4Compound；
3rd, TiO2-FG-ZnBi2O4The preparation of compound：
1）By gained FG-ZnBi2O4Compound 1g ultrasonic disperse 60min in absolute ethyl alcohol, then under the conditions of magnetic agitation
Butyl titanate 0.5g is added, continues to stir after 30 min, mixed liquor is transferred in polytetrafluoroethylliner liner, load stainless steel
Reactor, the h of insulation reaction 12 at 180 DEG C；
2）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing 60 DEG C of dryings in vacuum drying chamber, obtain TiO2-FG-ZnBi2O4Compound.
After testing, present invention gained TiO2-FG-ZnBi2O4Composite visible light response catalyst is multilayer chip structure, its
Lamellar spacing is about 17 nm, and the main presence in the form of C-F keys of the fluorine atom in graphene.
By gained TiO2-FG-ZnBi2O4Composite visible light response catalyst 0.1g is placed in the idol that 100mL concentration is 50mg/L
In nitrogen type organic pollutant solution, 10min is reacted under visible light illumination, and its degradation rate can reach more than 99%, and the same terms
Lower catalyst is reused 5 catalytic effects and is not decreased obviously.Prove composite visible light response catalyst of the present invention to organic
Pollutant has good catalytic degradation activity and stability, reusable.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of preparation method of fluorinated graphene composite visible light response catalyst, it is characterised in that：Comprise the following steps：
Step 1: FG preparation：
1）By graphene oxide ultrasonic disperse in deionized water, graphene oxide dispersion is obtained；
2）Gained graphene oxide dispersion is added in the water heating kettle with polytetrafluoroethyllining lining, fluorination is then added
Sodium, insulation reaction 3-12h at 180 DEG C；
3）After question response terminates, it is allowed to naturally cool to room temperature, then by reacting liquid filtering, filter cake is repeatedly washed with ultra-pure water,
Until cleaning solution pH value reaches neutrality, then gained solid product is dried, FG is obtained；
Step 2: FG-ZnBi2O4The preparation of compound：
1）Absolute ethyl alcohol is added to be configured to mixed solution bismuth nitrate and zinc nitrate；
2）By gained FG ultrasonic disperses in absolute ethyl alcohol, prepared mixed solution is then added under the conditions of magnetic agitation,
Continue to stir after 30 min, be transferred into polytetrafluoroethylliner liner, load insulation reaction at stainless steel cauldron, 180 DEG C
3-12h；
3）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing obtains FG-ZnBi in 60 DEG C of dryings2O4Compound；
Step 3: TiO2-FG-ZnBi2O4The preparation of compound：
1）By gained FG-ZnBi2O4Then compound ultrasonic disperse adds metatitanic acid in absolute ethyl alcohol under the conditions of magnetic agitation
Four butyl esters, continue to stir after 30 min, mixed liquor are transferred in polytetrafluoroethylliner liner, load stainless steel cauldron, 180 DEG C
Lower insulation reaction 3-12 h；
2）Product is taken out after reaction, with washes of absolute alcohol twice first, then is cleaned twice with deionized water, will finally be produced
Thing obtains TiO in 60 DEG C of dryings2-FG-ZnBi2O4Compound, as described fluorinated graphene composite visible light response catalyst.
2. the preparation method of fluorinated graphene composite visible light response catalyst according to claim 1, it is characterised in that：Step
The weight ratio of graphene oxide and sodium fluoride is 1 in rapid one:0.01-0.05.
3. the preparation method of fluorinated graphene composite visible light response catalyst according to claim 1, it is characterised in that：Step
The weight ratio of FG and bismuth nitrate, zinc nitrate is 1 in rapid two:0.1-0.5:0.3-0.8.
4. the preparation method of fluorinated graphene composite visible light response catalyst according to claim 1, it is characterised in that：Step
FG-ZnBi in rapid three2O4The weight ratio of compound and butyl titanate is 1:0.5.
5. the preparation method of fluorinated graphene composite visible light response catalyst according to claim 1, it is characterised in that：Behaviour
In work, the time of ultrasonic disperse is 30-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710101141.6A CN106964378B (en) | 2017-02-24 | 2017-02-24 | A kind of preparation method of fluorinated graphene composite visible light response catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710101141.6A CN106964378B (en) | 2017-02-24 | 2017-02-24 | A kind of preparation method of fluorinated graphene composite visible light response catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106964378A true CN106964378A (en) | 2017-07-21 |
| CN106964378B CN106964378B (en) | 2019-07-09 |
Family
ID=59328306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710101141.6A Active CN106964378B (en) | 2017-02-24 | 2017-02-24 | A kind of preparation method of fluorinated graphene composite visible light response catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106964378B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363601A (en) * | 2020-03-13 | 2020-07-03 | 中国科学院宁波材料技术与工程研究所 | Fluorinated graphene oxide/titanium dioxide nano lubricating additive, preparation method and application |
| CN114247442A (en) * | 2021-12-24 | 2022-03-29 | 安徽工业大学 | Fluorine-doped graphene loaded CuO composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561971A (en) * | 2015-12-16 | 2016-05-11 | 大连民族大学 | Novel visible light responsive photocatalyst ZnBi2O4 nanosphere as well as preparation method and application of novel visible light responsive photocatalyst ZnBi2O4 nanosphere in pollutant detection |
-
2017
- 2017-02-24 CN CN201710101141.6A patent/CN106964378B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561971A (en) * | 2015-12-16 | 2016-05-11 | 大连民族大学 | Novel visible light responsive photocatalyst ZnBi2O4 nanosphere as well as preparation method and application of novel visible light responsive photocatalyst ZnBi2O4 nanosphere in pollutant detection |
Non-Patent Citations (1)
| Title |
|---|
| 郭肖娜等: ""钒酸铋/二氧化钛-石墨烯宽光谱复合光催化剂的制备及性能"", 《工程科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363601A (en) * | 2020-03-13 | 2020-07-03 | 中国科学院宁波材料技术与工程研究所 | Fluorinated graphene oxide/titanium dioxide nano lubricating additive, preparation method and application |
| CN111363601B (en) * | 2020-03-13 | 2022-04-29 | 中国科学院宁波材料技术与工程研究所 | Fluorinated graphene oxide/titanium dioxide nano lubricating additive, preparation method and application |
| CN114247442A (en) * | 2021-12-24 | 2022-03-29 | 安徽工业大学 | Fluorine-doped graphene loaded CuO composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106964378B (en) | 2019-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103599800B (en) | The preparation method of glass fiber loaded silver-silver bromide-titanium oxide composite material | |
| CN111921550B (en) | MXene/titanium dioxide nanotube composite photocatalyst and preparation method thereof | |
| CN111056567B (en) | Preparation method of black rutile phase titanium dioxide | |
| CN102302955B (en) | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof | |
| CN104707632A (en) | Visible light responsive Ag-AgBr/Bi20TiO32 composite photocatalyst as well as preparation method and application thereof | |
| CN105214689A (en) | A kind of TiO 2/ CdS/ Graphene composite photocatalyst material and preparation method thereof | |
| CN101862662A (en) | Multi-doped half-load type Fenton-assisting titanium dioxide photochemical catalyst as well as preparation method and application method | |
| CN106563477A (en) | Ternary composite visible light photocatalyst, preparation method and application thereof | |
| CN102125859A (en) | Preparation method of p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst | |
| CN106622293A (en) | Preparation method of H-TiO2/CdS/Cu(2-x)S nanoribbon | |
| CN106964378B (en) | A kind of preparation method of fluorinated graphene composite visible light response catalyst | |
| CN105772045B (en) | A kind of BiPO4‑ZnFe2O4Composite photo-catalyst and preparation method thereof | |
| CN107876039A (en) | The preparation method of graphene cerium oxide hybrid material | |
| CN112473712A (en) | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN102357360A (en) | Catalyst for degrading rhodamine B by photocatalysis, and preparation method thereof | |
| CN103349982B (en) | Bi2WO6 modified TiO2 nanobelt photocatalyst, preparation method and application thereof | |
| CN102389836B (en) | Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof | |
| CN105854912A (en) | BiPO4-WO3 composite photocatalyst and preparation method thereof | |
| CN114849752A (en) | Hexagonal boron nitride/flower ring-shaped graphite type carbon nitride heterojunction composite photocatalyst and preparation method and application thereof | |
| CN110586149B (en) | Bismuth molybdate/titanium carbide heterojunction two-dimensional photocatalytic material and preparation method and application thereof | |
| CN104324743A (en) | Preparation method of nitrogen-doped TiO2 nanotube composite Fe2O3 catalyst | |
| CN106881154A (en) | A kind of polyaniline bismuth molybdate heterojunction photocatalyst and preparation method and application | |
| CN111359648A (en) | HTiNbO5nanosheet/g-C3N4Multifunctional composite photocatalyst and preparation method thereof | |
| CN103864594A (en) | C/TiO2 photocatalytic reduction method of carbon dioxide | |
| CN107626298B (en) | Bismuth semiconductor photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240325 Address after: Room 1403, Unit 2, Building 1, No. 288, Huangdao District (formerly Zhuhai East Road), Qingdao City, Shandong Province, 266000 Patentee after: Qingdao Jiaze Maosheng Information Technology Co.,Ltd. Country or region after: China Address before: 365004, No. 25 Jing Dong Road, three yuan, Fujian, Sanming City Patentee before: SANMING University Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240412 Address after: No. 3600 Haixi Road, Huangdao District, Qingdao City, Shandong Province, 266000 Patentee after: Qingdao Xinding Wanxing New Material Co.,Ltd. Country or region after: China Address before: Room 1403, Unit 2, Building 1, No. 288, Huangdao District (formerly Zhuhai East Road), Qingdao City, Shandong Province, 266000 Patentee before: Qingdao Jiaze Maosheng Information Technology Co.,Ltd. Country or region before: China |