CN108212160A - A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation - Google Patents
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 230000010358 mechanical oscillation Effects 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000000017 hydrogel Substances 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000696 magnetic material Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000258920 Chilopoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000270322 Lepidosauria Species 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/61—
Abstract
The present invention relates to a kind of preparation methods of the magnetic oxygenated graphene composite material of photocatalytic degradation, include the following steps：Prepare graphene oxide dispersion, prepare the magnetic core of package graphene oxide, by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphene composite material of different catalysts content is made, the present invention is wrapped with graphene oxide sheet outside magnetic core, effectively improve the specific surface area of magnetic material, utilize the suction-operated of magnet and magnetic core, photochemical catalyst can effectively be recycled, hydroxyl and hydroxyl on graphene oxide, the affinity with water can be enhanced, the dispersibility of enhancing catalyst body in water is conducive to effective progress of catalytic action.
Description
Technical field
The present invention relates to photocatalysis technology fields, and in particular to a kind of magnetic oxygenated graphene composite wood of photocatalytic degradation
The preparation method of material.
Background technology
Photocatalytic pollutant degradation technology is to utilize the pollutant in all kinds of waste water of semiconductor light-catalyst processing, photocatalysis
Agent has very strong oxidisability, being capable of effectively light for the substance difficult to degrade such as dyestuff, surfactant, organohalogen compounds
Catalysis reaction, and have good degradation effect, reach permineralization, therefore in organic matter difficult to degrade of degrading by sustained response
Tool has very important significance in terms of pollution.
Semiconductor with multinomial photocatalysis performance includes WO3、TiO2、CdS、ZnO、Fe2O3, CdSe, Bi etc., wherein by
In TiO2With anti-chemistry and photoetch, property stabilization, the five poisonous creatures: scorpion, viper, centipede, house lizard, toad, catalytic activity it is high, it is cheap etc. a little, and have attracted much attention.
Currently used TiO2Film preparation is on solid carrier mountain, but there are catalytic performance is high, easy fracture, film are easily de- for film obtained
The problem of falling, and there is be difficult to disperse, be difficult to separate and recover, not high to sun light utilization ratio for single nano-photocatalyst
Etc. a series of shortcoming.The wherein separation and recovery of nano-photocatalyst and the catalytic activity improved under visible light is always light
The key points and difficulties of catalytic field research.
Recently, have in terms of photochemical catalyst recycles and improves the activity of photochemical catalyst through load technology, both avoided
The reunion of catalyst granules itself, and facilitate recycling；For another example by the way that photochemical catalyst to be coated to the surface of magnetic material, shape
Core is done into magnetic material, photochemical catalyst does the structure of shell, and the purpose of separation and recovery is realized by magnetic field.But the table of magnetic material
Face effect is bad, and specific surface area is small, it is impossible to effectively adsorb TiO2So that its photocatalysis is small.
Invention content
To overcome the deficiency, the magnetic oxygenated graphene the purpose of the present invention is to provide a kind of photocatalytic degradation is compound
The preparation method of material, effectively improves the specific surface area of magnetic material, and magnetic core can effectively recycle photochemical catalyst, enhance
Dispersibility in water.
The technical solution adopted by the present invention to solve the technical problems is：A kind of magnetic oxygenated graphene of photocatalytic degradation
The preparation method of composite material, includes the following steps：
Step 1: prepare graphene oxide dispersion
A certain amount of graphene oxide is added in into supersonic oscillations 1-2 hours in 50mL ethyl alcohol, adds 20mL hydrochloric acid and 10
ML deionized waters continue sonic oscillation 1-2h, and the GO solution of 2-4g/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 3-5min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again,
Graphene oxide is made to be wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
Alkene composite material, its implementation include following two methods：
（1）After step 2 and then 0.3-0.4g ammonium sulfate stirring 5min is added in, then four fourth of 3.5-5 mL metatitanic acids is slowly added dropwise
3h is stirred after ester, gained mixed solution is moved into water heating kettle later, is placed in air dry oven the isothermal reaction under certain temperature
For 24 hours, after reaction, reaction final product ethyl alcohol and deionized water are washed to neutrality, most after 60 DEG C of drying, are prepared into
To the magnetic oxygenated graphene composite material of different catalysts content.
（2）By the magnetic core graphene oxide solution obtained by the step 2, hydro-thermal reaction is carried out in the case where protecting gas, is reacted
Temperature is 120-240 DEG C, and the time is 10-24 hours, and protection gas is obtained hydrogel after the completion of reaction, be freeze-dried using nitrogen
Afterwards, obtain being enclosed with the graphene oxide powder of magnetic core, because hydrogel is in the case where being dialysed, water during freezing
Become ice, ice crystal is grown up comparatively fast, can burst the three-dimensional netted graphene oxide that hydrogel is formed, and then obtains powder dress
The graphene oxide of magnetic core is enclosed with, adds ammonium titanium fluoride and boric acid, heating hydrolysis generation nano-titanium dioxide loads to
On graphene oxide, after vacuum drying, then 2h is calcined at 200 DEG C.
Specifically, the graphene oxide uses sheet graphene oxide.
Specifically, the magnetisable material uses nanometer Fe3O4Or ZnFe2O3。
Specifically, the Fe3O4Preparation method is by FeCl3•6H2O、FeCl2•4H2O and NaCl are dissolved in deionized water
In, solution surface slowly covers one layer of oil film, then to being slowly added to sodium hydroxide solution, then carry out magnetic agitation, after stirring
Nano particle therein is detached, isolated particle is cleaned with deionized water, is centrifuged, is obtained sample,
And obtained sample is freeze-dried successively, encapsulates preservation, obtain nano ferriferrous oxide.
Specifically, the ZnFe2O3Preparation method be by zinc salt and molysite, wherein the molar ratio of zinc and iron is 1：2, it is molten
In absolute ethyl alcohol, 0.5-12h is stirred at room temperature, and pH to 9-10 is adjusted with NaOH solution；It is stirred at room temperature, is transferred to interior
90~250 DEG C of reactions in the water heating kettle of lining teflon, react 5-10 hours, after cooled to room temperature, are detached with magnet,
Water washing is distilled, 60 DEG C are dried in vacuo 24 hours, and nanometer Zn Fe is made2O3。
The invention has the advantages that：Graphene oxide sheet is wrapped with outside magnetic core, effectively improves magnetic material
Specific surface area, using the suction-operated of magnet and magnetic core, can effectively recycle photochemical catalyst, the hydrogen on graphene oxide
Oxygen root and hydroxyl, can enhance the affinity with water, and the dispersibility of enhancing catalyst body in water is conducive to catalytic action
Effectively carry out.
Specific embodiment
The present invention is described in further detail now.
Embodiment one
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
The graphene oxide of 0.1g is added in into supersonic oscillations 1-2 hours in 50mL ethyl alcohol, adds 20mL hydrochloric acid and 10 mL
Deionized water continues sonic oscillation 1h, and the GO solution of 2mg/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 3min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
Alkene composite material after step 2 and then adds in 0.3g ammonium sulfate stirring 5min, then 3.5 mL butyl titanates are slowly added dropwise
After stir 3h, later by gained mixed solution move into water heating kettle, be placed in air dry oven the isothermal reaction under certain temperature
For 24 hours, after reaction, reaction final product ethyl alcohol and deionized water are washed to neutrality, most after 60 DEG C of drying, are prepared into
To the magnetic oxygenated graphene composite material containing photochemical catalyst.
Specifically, the graphene oxide uses sheet graphene oxide.
Specifically, the magnetisable material uses nanometer Fe3O4Or ZnFe2O3。
Specifically, the Fe3O4Preparation method is by FeCl3•6H2O、FeCl2•4H2O and NaCl are dissolved in deionized water
In, solution surface slowly covers one layer of oil film, then to being slowly added to sodium hydroxide solution, then carry out magnetic agitation, after stirring
Nano particle therein is detached, isolated particle is cleaned with deionized water, is centrifuged, is obtained sample,
And obtained sample is freeze-dried successively, encapsulates preservation, obtain nano ferriferrous oxide.
Specifically, the ZnFe2O3Preparation method be by zinc salt and molysite, wherein the molar ratio of zinc and iron is 1：2, it is molten
In absolute ethyl alcohol, 0.5-12h is stirred at room temperature, and pH to 9-10 is adjusted with NaOH solution；It is stirred at room temperature, is transferred to interior
90~250 DEG C of reactions in the water heating kettle of lining teflon, react 5-10 hours, after cooled to room temperature, are detached with magnet,
Water washing is distilled, 60 DEG C are dried in vacuo 24 hours, and nanometer Zn Fe is made2O3。
Embodiment two
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
0.2g graphene oxides are added in into supersonic oscillations 2 hours in 50mL ethyl alcohol, add 20mL hydrochloric acid and 10 mL go from
Sub- water continues sonic oscillation 2h, and the GO solution of 4mg/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 5min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
Alkene composite material after step 2 and then adds in 0.4g ammonium sulfate stirring 5min, then after 5 mL butyl titanates are slowly added dropwise
3h is stirred, gained mixed solution is moved into water heating kettle later, is placed in air dry oven under certain temperature isothermal reaction for 24 hours,
After reaction, reaction final product ethyl alcohol and deionized water are washed to neutrality, most after 60 DEG C of drying, is prepared and contains
There is the magnetic oxygenated graphene composite material of photochemical catalyst.
Embodiment three
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
0.15g graphene oxides are added in into supersonic oscillations 1.5 hours in 50mL ethyl alcohol, 20mL hydrochloric acid is added and 10 mL is gone
Ionized water continues sonic oscillation 1.5h, and the GO solution of 3mg/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 4min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
Alkene composite material after step 2 and then adds in 0.3-0.4g ammonium sulfate stirring 5min, then 3.5-5 mL metatitanic acids are slowly added dropwise
3h is stirred after four butyl esters, gained mixed solution is moved into water heating kettle later, is placed in air dry oven the constant temperature under certain temperature
For 24 hours, after reaction, reaction final product ethyl alcohol and deionized water are washed to neutrality, most after 60 DEG C of drying, system for reaction
It is standby to obtain the magnetic oxygenated graphene composite material containing photochemical catalyst.
Example IV
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
0.15g graphene oxides are added in into supersonic oscillations 1-2 hours in 50mL ethyl alcohol, 20mL hydrochloric acid is added and 10 mL is gone
Ionized water continues sonic oscillation 1-2h, and the GO solution of 3mg/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 4min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
By the magnetic core graphene oxide solution obtained by the step 2, hydro-thermal reaction is carried out in the case where protecting gas for alkene composite material, reaction
Temperature is 120 DEG C, and the time is 24 hours, and protection gas is obtained hydrogel after the completion of reaction, after freeze-drying, obtained using nitrogen
The graphene oxide powder of magnetic core is enclosed with, adds in ammonium titanium fluoride and boric acid, heating hydrolysis generation nano-titanium dioxide, load
Onto graphene oxide, after vacuum drying, then 2h is calcined at 200 DEG C, the magnetic oxygenated stone containing photochemical catalyst is prepared
Black alkene composite material.
Embodiment five
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
0.1g graphene oxides are added in into supersonic oscillations 1-2 hours in 50mL ethyl alcohol, 20mL hydrochloric acid is added and 10 mL is gone
Ionized water continues sonic oscillation 1-2h, and the GO solution of 2-4g/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 5min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
By the magnetic core graphene oxide solution obtained by the step 2, hydro-thermal reaction is carried out in the case where protecting gas for alkene composite material, reaction
Temperature is 240 DEG C, and the time is 10 hours, and protection gas is obtained hydrogel after the completion of reaction, after freeze-drying, obtained using nitrogen
The graphene oxide powder of magnetic core is enclosed with, adds in ammonium titanium fluoride and boric acid, heating hydrolysis generation nano-titanium dioxide, load
Onto graphene oxide, after vacuum drying, then 2h is calcined at 200 DEG C, the magnetic oxygenated stone containing photochemical catalyst is prepared
Black alkene composite material..
Embodiment six
A kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, includes the following steps：
Step 1: prepare graphene oxide dispersion
0.2g graphene oxides are added in into supersonic oscillations 1-2 hours in 50mL ethyl alcohol, add 20mL hydrochloric acid and 10mL go from
Sub- water continues sonic oscillation 1-2h, and the GO solution of 3mg/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, adds in EDA reducing agents, the container sealing of solution will be contained
Afterwards, mechanical oscillation 4min avoids viscosity after adding in EDA from increasing, avoids mixed solution wadding heavy, then carry out magnetic agitation again, make
Graphene oxide is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
By the magnetic core graphene oxide solution obtained by the step 2, hydro-thermal reaction is carried out in the case where protecting gas for alkene composite material, reaction
Temperature is 160 DEG C, and the time is 18 hours, and protection gas is obtained hydrogel after the completion of reaction, after freeze-drying, obtained using nitrogen
The graphene oxide powder of magnetic core is enclosed with, adds in ammonium titanium fluoride and boric acid, heating hydrolysis generation nano-titanium dioxide, load
Onto graphene oxide, after vacuum drying, then 2h is calcined at 200 DEG C, the magnetic oxygenated stone containing photochemical catalyst is prepared
Black alkene composite material..
The present invention is not limited to the embodiment, anyone should learn that the structure made under the enlightenment of the present invention becomes
Change, the technical schemes that are same or similar to the present invention are each fallen within protection scope of the present invention.
The present invention be not described in detail technology, shape, construction part be known technology.
Claims (7)
1. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation, it is characterised in that：Including following step
Suddenly：
Step 1: prepare graphene oxide dispersion
A certain amount of graphene oxide is added in into supersonic oscillations 1-2 hours in ethyl alcohol, add 20mL hydrochloric acid and 10mL go from
Sub- water continues sonic oscillation 1-2h, and the GO solution of 2-4g/mL, i.e. graphene oxide solution is made；
Step 2: prepare the magnetic core of package graphene oxide
Magnetic nuclear matter is added in step 1 in GO solution obtained, magnetic agitation is then carried out again, makes graphene oxide
It is wrapped in magnetic core, forms magnetic core graphene oxide solution；
Step 3: by catalyst scattered adsorption in graphene oxide layer, the magnetic oxygenated graphite of different catalysts content is made
Alkene composite material.
2. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 1,
It is characterized in that：In the step 2, EDA reducing agents are added in, after the container sealing for containing solution, mechanical oscillation 3-5min.
3. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 1,
It is characterized in that：The catalyst scattered adsorption of the step 3 is in the implementation method of graphene oxide layer, right after step 2
0.3-0.4g ammonium sulfate stirring 5min is added in afterwards, then stirs 3h after 3.5-5mL butyl titanates are slowly added dropwise, and later mixes gained
It closes solution and moves into water heating kettle, being placed in air dry oven the isothermal reaction under certain temperature for 24 hours, after reaction, will react most
Final product ethyl alcohol and deionized water are washed to neutrality, and most after 60 DEG C of drying, the magnetism of different catalysts content is prepared
Graphene oxide composite material.
4. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 1,
It is characterized in that：The catalyst scattered adsorption of the step 3 is in the implementation method of graphene oxide layer, by the step 2 institute
The magnetic core graphene oxide solution obtained, hydro-thermal reaction is carried out in the case where protecting gas, and protection gas is obtained using nitrogen after the completion of reaction
Hydrogel after freeze-drying, obtains being enclosed with the graphene oxide powder of magnetic core, adds in ammonium titanium fluoride and boric acid, heats water
Solution generation nano-titanium dioxide, loads on graphene oxide, after vacuum drying, then calcines 2h at 200 DEG C.
5. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 4,
It is characterized in that：The hydrothermal temperature is 120-240 DEG C, and the time is 10-24 hours.
6. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 1,
It is characterized in that：The graphene oxide uses sheet graphene oxide.
7. a kind of preparation method of the magnetic oxygenated graphene composite material of photocatalytic degradation according to claim 1,
It is characterized in that：The magnetisable material uses nanometer Fe3O4Or ZnFe2O3。
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