CN107913667A - A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application - Google Patents
A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application Download PDFInfo
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- CN107913667A CN107913667A CN201711008658.7A CN201711008658A CN107913667A CN 107913667 A CN107913667 A CN 107913667A CN 201711008658 A CN201711008658 A CN 201711008658A CN 107913667 A CN107913667 A CN 107913667A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 89
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 14
- 229940056319 ferrosoferric oxide Drugs 0.000 title claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- 230000004044 response Effects 0.000 claims abstract description 3
- 230000002459 sustained effect Effects 0.000 claims abstract description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 17
- 238000006392 deoxygenation reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000975 dye Substances 0.000 description 25
- 206010001497 Agitation Diseases 0.000 description 20
- 238000013019 agitation Methods 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 229960000907 methylthioninium chloride Drugs 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation method and application, prepares as follows：(1) graphene oxide, polyethylene glycol are dispersed in pure water in water bath with thermostatic control, are ultrasonically formed uniform suspension：(2) FeCl is added dropwise3And FeCl2, when sustained response 4~6 is small under oxygen-free environment, then add ammonium hydroxide tune pH to 10.5~11.5, rise bath temperature to 70~80 DEG C, the reaction was continued 2~3 it is small when, obtain mixed liquor；(3) MnSO is added into gained mixed liquor4Solution, then adds KMnO4And KOH, when reaction 2~4 is small, then post-processed to obtain the final product.The present invention is using graphene sheet layer as carrier, and in-situ precipitate grows Fe on graphene sheet layer successively3O4And MnO2Nano-particle, prevents the reunion of graphene；At the same time Fe is used as by the use of the lamellar structure of graphene oxide3O4And MnO2Nano-particle immobilization carrier, to prevent Fe3O4And MnO2The reunion of nano-particle.Nanocomposite method provided by the invention has the characteristics that environmentally protective, fast and convenient.
Description
Technical field
The invention belongs to nano material and technical field of environmental science, more particularly to one kind to have absorption and catalytic degradation work(
The magnetic rGO/Fe of energy3O4/MnO2Nanocomposite and its application.
Background technology
Dyestuff is widely used in the industries such as weaving, leather, papermaking, printing and cosmetics, according to statistics the annual output of China's dyestuff
About 750,000 tons of amount, occupies first place in the world.Dyestuff there are about 10~15% in the production and use process can be discharged into environment, because of dyestuff
Water body safety problem has caused extensive concern caused by pollution.Usual dye molecule is very stable with complicated aromatic structure,
It is difficult natural degradation in water environment.At present, the processing method of waste water from dyestuff mainly has absorption method, membrane separation process, and catalysis oxidation
Degraded etc..Absorption method is the important technology of Sewage advanced treatment, and in numerous adsorbents, activated carbon has been widely used dyestuff and gives up
In water process.But activated carbon there are adsorbance is little, activation temperature is high, pore size distribution is wide, bad mechanical property, be not easy regeneration and table
Face is not easy the shortcomings of modification.Carbon nanomaterial, because it is with high specific surface area and good chemical stability, in waste water
Huge potentiality and tempting application prospect are shown in the absorption of pollutant.
Graphene is a kind of New Two Dimensional nano material, and specific surface area is big, and theoretical calculation reaches 2630m2/ g, has superpower
Adsorption capacity.Ramesha etc. (Ramesha G K, Vijaya Kumara A, Muralidhara H B, Sampath S,
Graphene and Graphene Oxide as Effective Adsorbents Toward Anionic and
Cationic Dyes, Journal of Colloid and Interface Science, 2011,361,270-277) research
It was found that very strong complex reaction can be produced between graphene and organic dyestuff, so as to there is very strong absorption to organic dyestuff
Ability.But due to the nano-lamellar structure of graphene, more difficult separation, recycling in water body, be easily leaked in environment cause it is strong
Health and environmental problem.Further, since easily reuniting in water body there are model ylid bloom action between graphene sheet layer, cause effective table
Area is reduced, so as to reduce adsorption capacity.Therefore the graphene or graphene composite material that exploitation has hydrophily, easily recycles,
It is the research and development direction of the novel adsorption functional material based on graphene.
(Zhao Guixia, Jiang, Lang He, Yu dong, Li Jiaxing, the Dong Huanli, Wang such as Wang
Xiangke,Hu Wenping,Sulfonated Graphene for Persistent Aromatic Pollutant
Management, Advanced Materials, 2011,23 (34), 3959-3963) sulfonic group parent is carried out to graphene surface
Water functionalization, can not only improve the dispersiveness of graphene, and can improve the adsorption capacity of graphene.Result of study
It has been shown that, this functionalization graphene has reached every gram of 2.4mmol to the adsorption capacity of naphthalene and naphthols, is that current adsorption capacity is higher
Material.
Magnetic adsorptive material not only has good adsorption capacity, but also can be separated by externally-applied magnetic field from water body, has become
The material of new generation of environment in recent years purification.
Catalyzing oxidizing degrading is also one of removal organic polluter effective ways.Compared to absorption method, catalytic oxidation profit
With the organic pollution in catalyst degradation water body, so as to achieve the purpose that environmental improvement.MnO2With higher oxidizing potential,
Many organic compounds can be aoxidized, are widely used in as oxidant in water process.But MnO2Apparent density it is smaller, in water
In easily formed ultra-fine grain, be difficult to realize separation of solid and liquid after use.
The content of the invention
The present invention provides a kind of magnetism rGO/Fe3O4/MnO2Nanocomposite and its preparation method and application, composite wood
Material has the function of absorption and catalytic degradation well.
A kind of preparation method of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material, including following step
Suddenly：
Graphene oxide, polyethylene glycol are dispersed in pure water in (1) 20~40 DEG C of water bath with thermostatic control, are ultrasonically formed uniformly
Suspension：
(2) suspension is continued persistently to stir in 20~40 DEG C of waters bath with thermostatic control and FeCl is added dropwise after deoxygenation3With
FeCl2Mixed solution, when sustained response 4~6 is small under oxygen-free environment, then add ammonium hydroxide tune pH to 10.5~11.5, accelerate
Mixing speed, rise bath temperature to 70~80 DEG C, the reaction was continued 2~3 it is small when, rGO/Fe must be contained3O4Mixed liquor；
(3) it is kept stirring speed and bath temperature is constant, MnSO is added into gained mixed liquor4Solution, it is then quick again
Add KMnO4With the mixed solution of KOH, when reaction 2~4 is small, obtain including rGO/Fe3O4/MnO2Mixed liquor；
(4) rGO/Fe will be contained3O4/MnO2Mixed liquor repeated filtration, wash after in 140~160 DEG C of vacuum drying chambers
When heat treatment 20~25 is small to obtain the final product.
The present invention is using graphene sheet layer as carrier, and in-situ precipitate grows Fe on graphene sheet layer successively3O4And MnO2Nanometer
Particle, utilizes the Fe of growth in situ3O4And MnO2Nano-particle prevents the reunion of graphene；The piece of graphene oxide is utilized at the same time
Rotating fields are as Fe3O4And MnO2Nano-particle immobilization carrier, to prevent Fe3O4And MnO2The reunion of nano-particle.
The present invention selects FeCl first using GO as carrier3And FeCl2For presoma, PEG is reducing agent and nano-particle point
Dispersion stabilizer, rGO/Fe is prepared using the precipitation method3O4Nano-complex, then with MnSO4And KMnO4For presoma, pass through the precipitation method
Prepare rGO/Fe3O4/MnO2Nanocomposite.RGO/Fe prepared by the present invention3O4/MnO2Nanocomposite gives up for dyestuff
The absorption of water and photocatalytic degradation remove, and show preferable removal capacity, and separate, return from water body using externally-applied magnetic field
Receive.
The novel part of the present invention shows as the rGO/Fe prepared3O4/MnO2Nanocomposite, passes through GO, Fe3O4With
MnO2Nano combined and synergistic effect, nanocomposite be not only provided with excellent Dye Adsorption ability, but also with good
Good Photocatalytic Degradation Property, while also there is certain magnetism, separate, recycle from water body using externally-applied magnetic field.This hair
The rGO/Fe of bright offer3O4/MnO2Nanocomposite method has the characteristics that environmentally protective, fast and convenient.
Preferably, the GO mass that is added in step (1) and pure water volume ratio are 1/1.5~1/2.0mg/mL, oxygen in GO
Content for 4.5~6.5%, GO can by commercially available acquisition, the methods of Hummers can also be used (D.C.Marcano,
D.V.Kosynkin,J.M.Berlin,et al.Improved synthesis of graphene oxid[J].ACS
Nano,2010,4:4806-4814) prepared；The PEG added and GO mass ratioes are 5~10, PEG preferred PEG-400, PEG-
600、PEG-800。
Graphene oxide quality and the ratio of pure water volume are more preferably 1mg in step (1)：1.7~1.8mL.
Preferably, FeCl in step (2)2It is 1/1~1.5/1 with GO mass ratioes；FeCl3With FeCl2Molar ratio is 2/1.
Preferably, MnSO in step (3)4With FeCl2And FeCl3Total mass ratio is 0.6/1~0.75/1；KMnO4With MnSO4
Mass ratio is 1/1.1~1/1.2；KOH and MnSO4And KMnO4Total mass ratio is 0.9/1~1/1.
Preferably, ultrasonic time is 45~60min in step (1), when being more preferably 1 small.
Preferably, mixing speed is 1400~1600rpm in 20~40 DEG C of waters bath with thermostatic control in step (2)；70~80 DEG C of perseverances
Mixing speed is 2800~3200rpm in tepidarium.
Preferably, the ammonia spirit that ammonium hydroxide used is 25mg/mL in step (2).
Preferably, water bath with thermostatic control temperature is 30 DEG C in step (1)；It is 30 DEG C that heating is preceding in step (2), is 75 after heating
℃。
It is further preferred that mixing speed is 1500rpm in 30 DEG C of waters bath with thermostatic control in step (2)；In 75 DEG C of waters bath with thermostatic control
Mixing speed is 3000rpm.
It is further preferred that step (2) is：
Suspension obtained by step (1) leads to N under 1500rpm magnetic agitations, in 30 DEG C of water bath with thermostatic control2When deoxygenation 1 is small,
Then FeCl is slowly added dropwise3And FeCl2Mixed solution, FeCl2It is 1/1~1.5/1 with GO mass ratioes；The FeCl added3With
FeCl2Molar ratio is 2/1, continues to stir and lead to N2When deoxygenation 5 is small, it is molten and then to rapidly join the ammonium hydroxide that ammonia density is 25mg/mL
Liquid adjusts pH to 11 or so, then magnetic agitation is adjusted to 3000rpm, and bath temperature rises to 75 DEG C, when reaction 3 is small, comprising
There is rGO/Fe3O4Mixed liquor.
It is further preferred that step (3) is：
Under 3000rpm magnetic agitations, in 75 DEG C of water bath with thermostatic control MnSO is added into mixed liquor obtained by step (2)4Solution,
Then KMnO is rapidly joined again4With the mixed solution of KOH, when reaction 3 is small, obtain including rGO/Fe3O4/MnO2Mixed liquor,
MnSO4With FeCl2And FeCl3Total mass ratio is 0.6/1~0.75/1, the KMnO added4With MnSO4Mass ratio is 1/1.1~1/
1.2；, the KOH and MnSO that add4And KMnO4Total mass ratio is 0.9/1~1/1.
It is further preferred that step (4) is：
The mixed liquor obtained with bottle,suction to step (3) filters, and filter deposition thing is carried out repeatedly with pure water
Washing；To finally cross products therefrom after filter ﹑ washings be positioned in 150 DEG C of vacuum drying ovens heat treatment 24 it is small when, obtain rGO/Fe3O4/
MnO2Nanocomposite.
Compared with prior art, the invention has the advantages that：
The present invention prepares rGO/Fe using two-step precipitation3O4/MnO2Nanocomposite, in the preparation process of compound
In, Fe3O4And MnO2Nano-particle is grown in graphene film interlayer in-situ precipitate, utilizes the two-dimension plane structure of graphene oxide
Immobilized and scattered Fe3O4And MnO2Nano-particle, while prevent the reunion of graphene oxide layer.Prepared rGO/Fe3O4/
MnO2Nanocomposite, passes through GO, Fe3O4With MnO2Nano combined and mutual synergistic effect, show that excellent dyestuff is inhaled
Attached ability and Photocatalytic Degradation Property, while can be separated, recycled from water body with externally-applied magnetic field.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 1, comparative example 1, comparative example 2, comparative example 3, the nano combined material prepared by comparative example 4
Transmission electron microscope (TEM) photo of material.(A:Embodiment 1；B:Comparative example 1；C:Comparative example 2；D:Comparative example 3；E:Comparative example 4)
Fig. 2 is the embodiment of the present invention 1, comparative example 1, comparative example 2, the Raman of nanocomposite prepared by comparative example 4
Spectrum (Raman) figure.(embodiment 1:rGO/Fe3O4/MnO2(Ⅰ)；Comparative example 2:rGO/MnO2；Comparative example 1:rGO/Fe3O4；It is right
Ratio 4:rGO)
Fig. 3 is the embodiment of the present invention 1, the hysteresis curve of nanocomposite prepared by comparative example 1.(embodiment 1:
Fe3O4/MnO2/rGO(Ⅰ)；Comparative example 1:rGO/Fe3O4)
Embodiment
Be described below for of the invention more preferred embodiment, but be not used to limitation of the invention.
Further illustrated below by way of specific embodiment using how the present invention prepares rGO/Fe3O4/MnO2It is nano combined
Material, and its Dye Adsorption ability and Photocatalytic Degradation Property.
1.rGO/Fe3O4/MnO2The Dye Adsorption performance evaluation of nanocomposite：
Experiment chooses methylene blue (MB) and carries out rGO/Fe for object3O4/MnO2The absorption property of nanocomposite is commented
Valency, takes the pure water of the MB and 80mL of 8mg to be added to preparation MB solution in 250mL conical flasks, then that 50mg ultrasonic disperses is good
rGO/Fe3O4/MnO2It is added in above-mentioned mixed liquor, is put into 30 DEG C of water bath with thermostatic control magnetic agitations.Injected every 5min with disposable
Device draws the solution of 2mL, with 0.45 μm of membrane filtration, with the absorbance (λ=664nm) of spectrophotometric determination filtered fluid, leads to
The concentration that langbobier law calculates MB in filtered fluid is crossed, and the eliminating rate of absorption of MB is calculated by following formula.
Eliminating rate of absorption=(c0-ct)/c0
In formula, c0:The initial concentration of MB；ct:The concentration of MB after adsorbing t minutes.
2.rGO/Fe3O4/MnO2The dyestuff catalytic degradation performance evaluation of nanocomposite：
Experiment chooses methylene blue (MB) and carries out rGO/Fe for object3O4/MnO2The catalytic degradation of nanocomposite is commented
Valency, takes the pure water of the MB and 80ml of 8mg to be added to preparation MB solution in 250mL conical flasks, is adjusted with the HCl solution of 0.1mg/L
PH to 5.0, adds the good rGO/Fe of 50mg ultrasonic disperses3O4/MnO2, it is put into 30 DEG C of waters bath with thermostatic control magnetic agitation 30min extremely
Adsorption equilibrium, measures 2mL, 30%H2O2It is added in above-mentioned mixed liquor and reacts 60min.Inhaled every 5min with disposable syringe
The reaction solution of 2mL is taken, with 0.45 μm of membrane filtration, with the absorbance (λ=664nm) of spectrophotometric determination filtered fluid, is led to
The concentration that langbobier law calculates MB in filtered fluid is crossed, and the catalytic degradation removal rate of MB is calculated by following formula.
Catalytic degradation removal rate=(C0-Ct)/C0
In formula, C0:The initial concentration of MB；Ct:The concentration of MB after reacting t minutes.
Embodiment 1
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1000mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.Under 1500rpm magnetic agitations and logical N2When deoxygenation 1 is small, 30
It is respectively the FeCl of 100mg/mL (0.789mmol/mL), 256mg/mL (1.578mmol/mL) by concentration at DEG C2And FeCl3's
Mixed solution 2mL is slowly dropped in above-mentioned suspension, continues to stir and lead to N2When deoxygenation 5 is small, it is dense and then to rapidly join ammonia
Spend and adjust pH to 11 for the ammonium hydroxide of 25mg/mL, magnetic agitation speed is then adjusted to 3000rpm, water bath with thermostatic control temperature rises to 75
When reaction 3 is small at DEG C.Adding concentration into above-mentioned mixed liquor under the effect of 3000rpm magnetic agitations, in 75 DEG C of water bath with thermostatic control is
The MnSO of 120mg/mL4Solution 4mL, then rapidly join the KMnO that concentration is respectively 60mg/mL, 120mg/mL4With the mixing of KOH
Solution 7mL, when reaction 3 is small.The mixture of above-mentioned acquisition is filtered with bottle,suction, and spends pure water to filter deposition thing
Repeatedly washed；To finally cross products therefrom after filter ﹑ washings be positioned in 50 DEG C of vacuum drying ovens dry 24 it is small when, obtain rGO/
Fe3O4/MnO2Nanocomposite.
RGO/Fe prepared by the present embodiment3O4/MnO2A in transmission electron microscope (TEM) photo such as Fig. 1 of nanocomposite
It is shown；Prepared rGO/Fe3O4/MnO2Raman spectrum (Raman) figure of nanocomposite is referring to Fig. 2.
RGO/Fe prepared by the present embodiment3O4/MnO2The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table
1。
Embodiment 2
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1200mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.Under 1500rpm magnetic agitations and logical N2When deoxygenation 1 is small, 30
It is respectively the FeCl of 100mg/mL (0.789mmol/mL), 256mg/mL (1.578mmol/mL) by concentration at DEG C2And FeCl3's
Mixed solution 2.5mL is slowly dropped in above-mentioned suspension, continues to stir and lead to N2When deoxygenation 5 is small, ammonia is and then rapidly joined
The ammonium hydroxide that concentration is 25mg/mL adjusts pH to 11, magnetic agitation speed then is adjusted to 3000rpm, water bath with thermostatic control temperature rises to
When reaction 3 is small at 75 DEG C.Under the effect of 3000rpm magnetic agitations, concentration is added into above-mentioned mixed liquor in 75 DEG C of water bath with thermostatic control
For the MnSO of 120mg/mL4Solution 4.5mL, then rapidly join the KMnO that concentration is respectively 60mg/mL, 120mg/mL4With KOH's
Mixed solution 8mL, when reaction 3 is small.The mixture of above-mentioned acquisition is filtered with bottle,suction, and it is heavy to filtering to spend pure water
Product thing is repeatedly washed；To finally cross products therefrom after filter ﹑ washings be positioned in 50 DEG C of vacuum drying ovens dry 24 it is small when, obtain
rGO/Fe3O4/MnO2Nanocomposite.
RGO/Fe prepared by the present embodiment3O4/MnO2The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table
1。
Embodiment 3
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1400mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.Under 1500rpm magnetic agitations and logical N2When deoxygenation 1 is small, 30
It is respectively the FeCl of 100mg/mL (0.789mmol/mL), 256mg/mL (1.578mmol/mL) by concentration at DEG C2And FeCl3's
Mixed solution 3mL is slowly dropped in above-mentioned suspension, continues to stir and lead to N2When deoxygenation 5 is small, it is dense and then to rapidly join ammonia
Spend and adjust pH to 11 for the ammonium hydroxide of 25mg/mL, magnetic agitation speed is then adjusted to 3000rpm, water bath with thermostatic control temperature rises to 75
When reaction 3 is small at DEG C.Adding concentration into above-mentioned mixed liquor under the effect of 3000rpm magnetic agitations, in 75 DEG C of water bath with thermostatic control is
The MnSO of 120mg/mL4Solution 6mL, then concentration is rapidly joined to be respectively the KMnO of 60mg/mL, 120mg/mL4With mixing for KOH
Solution 11mL is closed, when reaction 3 is small.The mixture of above-mentioned acquisition is filtered with bottle,suction, and it is heavy to filtering to spend pure water
Product thing is repeatedly washed；To finally cross products therefrom after filter ﹑ washings be positioned in 50 DEG C of vacuum drying ovens dry 24 it is small when, obtain
rGO/Fe3O4/MnO2Nanocomposite.
RGO/Fe prepared by the present embodiment3O4/MnO2The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table
1。
Comparative example 1
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1000mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.Under 1500rpm magnetic agitations and logical N2When deoxygenation 1 is small, 30
It is respectively the FeCl of 100mg/mL (0.789mmol/mL), 256mg/mL (1.578mmol/mL) by concentration at DEG C2And FeCl3's
Mixed solution 2mL is slowly dropped in above-mentioned suspension, continues to stir and lead to N2When deoxygenation 5 is small, it is dense and then to rapidly join ammonia
Spend and adjust pH to 11 for the ammonium hydroxide of 25mg/mL, magnetic agitation speed is then adjusted to 3000rpm, water bath with thermostatic control temperature rises to 75
When reaction 3 is small at DEG C.The mixture of above-mentioned acquisition is filtered with bottle,suction, and spends pure water and filter deposition thing is carried out
Repeatedly washing；To finally cross products therefrom after filter ﹑ washings be positioned in 50 DEG C of vacuum drying ovens dry 24 it is small when, obtain rGO/Fe3O4
Nanocomposite.
RGO/Fe prepared by the present embodiment3O4Transmission electron microscope (TEM) photo of nanocomposite is as shown in B in Fig. 1；
Prepared rGO/Fe3O4Raman spectrum (Raman) figure of nanocomposite is referring to Fig. 2.
RGO/Fe prepared by the present embodiment3O4The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table 1.
Comparative example 2
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1200mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.Under the effect of 3000rpm magnetic agitations, 75 DEG C of water bath with thermostatic control
It is middle that the MnSO that concentration is 120mg/mL is added into above-mentioned suspension4Solution 4.5mL, then it is respectively 60mg/ to rapidly join concentration
The KMnO of mL, 120mg/mL4With the mixed solution 8mL of KOH, reaction 3 it is small when.The mixed liquor of above-mentioned acquisition is carried out with bottle,suction
Filtering, and spend pure water and filter deposition thing is repeatedly washed；The last products therefrom Jiang after Guo Lv ﹑ washings is positioned over 50 DEG C
When drying 24 is small in vacuum drying oven, rGO/MnO is obtained2Nanocomposite.
RGO/MnO prepared by the present embodiment2Transmission electron microscope (TEM) photo of nanocomposite is as shown in C in Fig. 1；
Prepared rGO/MnO2Raman spectrum (Raman) figure of nanocomposite is referring to Fig. 2.
RGO/MnO prepared by the present embodiment2The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table 1.
Comparative example 3
The PEG-600 for weighing 1400mg is dissolved in 350ml deionized waters, and uniform solution is formed when ultrasound 1 is small at 30 DEG C.
Under 1500rpm magnetic agitations and logical N2When deoxygenation 1 is small, at 30 DEG C by concentration be respectively 100mg/mL (0.789mmol/mL),
The FeCl of 256mg/mL (1.578mmol/mL)2And FeCl3Mixed solution 3mL be slowly dropped in above-mentioned solution, continue to stir
And logical N2When deoxygenation 5 is small, and then rapidly joins the ammonium hydroxide that ammonia density is 25mg/mL and adjust pH to 11, then by magnetic agitation
Speed is adjusted to 3000rpm, when water bath with thermostatic control temperature rises to that reaction 3 is small at 75 DEG C.Under the effect of 3000rpm magnetic agitations, 75 DEG C
The MnSO that concentration is 120mg/mL is added in water bath with thermostatic control into above-mentioned mixed liquor4Solution 6mL, then concentration is rapidly joined as difference
For the KMnO of 60mg/mL, 120mg/mL4With the mixed solution 11mL of KOH, reaction 3 it is small when.Mixed with bottle,suction to above-mentioned
Compound is filtered, and spends pure water and filter deposition thing is repeatedly washed；The last products therefrom Jiang after Guo Lv ﹑ washings is put
Be placed in 50 DEG C of vacuum drying ovens dry 24 it is small when, obtain Fe3O4/MnO2Nanocomposite.
Fe prepared by the present embodiment3O4/MnO2Transmission electron microscope (TEM) photo of nanocomposite is as shown in D in Fig. 1.
Fe prepared by the present embodiment3O4/MnO2The Dye Adsorption and catalytic degradation performance of nanocomposite are shown in Table 1.
Comparative example 4
The GO (oxygen-containing functional group is 5.2wt%) and the PEG-600 of 1000mg for weighing 200mg respectively are dissolved in 350ml
In ionized water, uniform suspension is formed when ultrasound 1 is small at 30 DEG C.The suspension of above-mentioned acquisition is filtered with bottle,suction,
And spend pure water and filter deposition thing is repeatedly washed；The last products therefrom Jiang after Guo Lv ﹑ washings is positioned over 50 DEG C of vacuum
When drying 24 is small in baking oven, rGO nano materials are obtained.
Transmission electron microscope (TEM) photo of rGO nano materials prepared by the present embodiment is as shown in E in Fig. 1.
Fig. 1 is rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2With the TEM photos of rGO.E can be seen that from Fig. 1
RGO is presented what is be completely exfoliated, translucent sheet yarn shape structure.D, C, B, A can be seen that Fe from Fig. 13O4/MnO2、Fe3O4、
MnO2It is in spherical nano-particle pattern, and Fe3O4、MnO2、Fe3O4/MnO2Nano-particle is all more evenly distributed in rGO pieces
On layer.
By Fig. 2 it can be seen that, rGO and rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2Raman spectrum all exist
1350cm-1And 1580cm-1There is defect, wherein 1350cm in place-1The defects of place peak (D peaks), what it reflected is carbon in rGO lamellas
Lattice defect, that is, sp of atom3Defect or amorphous carbon, 1580cm-1The defects of place peak (G peaks), it is corresponding, is rGO pieces
C atoms sp in layer2Stretching vibration in the face of hydridization.From the Raman spectrogram and its I of sampleD/IGValue can be clear from addition
Fe3O4、MnO2、Fe3O4/MnO2The I of rGO afterwardsD/IGValue increases, this is because being formed on rGO lamellas, particle diameter is smaller to be received
After rice corpuscles so that sp2Hydbridized carbon atoms average area reduces, and causes ID/IGValue rise.
Fig. 3 is embodiment 1, the hysteresis curve of nanocomposite prepared by comparative example 1, is shown prepared by this method
rGO/Fe3O4/MnO2、rGO/Fe3O4Stronger magnetism is respectively provided with, can be separated and recovered by externally-applied magnetic field from water body.
The Dye Adsorption and catalytic degradation performance of rGO nano materials prepared by the present embodiment are shown in Table 1.
Table 1 is the rGO/Fe prepared by the embodiment of the present invention3O4/MnO2Nanocomposite and comparative example 1, comparative example 2,
The Dye Adsorption and catalytic degradation performance of nanocomposite prepared by comparative example 3, comparative example 4.
Table 1
The rGO/Fe of embodiment 1-3 preparations is listed in table 1 respectively3O4/MnO2Nanocomposite, comparative example 1-4 difference
The rGO/Fe of preparation3O4Nanocomposite, rGO/MnO2Nanocomposite, Fe3O4/MnO2The MB of nanocomposite, GO
Eliminating rate of absorption and catalytic degradation removal rate.With rGO/Fe3O4Nanocomposite, rGO/MnO2Nanocomposite, Fe3O4/
MnO2Nanocomposite, GO are compared, rGO/Fe3O4/MnO2Nanocomposite is not only provided with excellent Dye Adsorption energy
Power, and there is good Photocatalytic Degradation Property, while also there is certain magnetism, divide using externally-applied magnetic field from water body
From, recycling.
Claims (8)
- A kind of 1. preparation method of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material, it is characterised in that bag Include following steps：Graphene oxide, polyethylene glycol are dispersed in pure water in (1) 20~40 DEG C of water bath with thermostatic control, are ultrasonically formed uniform outstanding Supernatant liquid；(2) suspension is continued persistently to stir in 20~40 DEG C of waters bath with thermostatic control and FeCl is added dropwise after deoxygenation3And FeCl2's Mixed solution, when sustained response 4~6 is small under oxygen-free environment, then adds ammonium hydroxide tune pH to 10.5~11.5, accelerates stirring speed Degree, rise bath temperature to 70~80 DEG C, the reaction was continued 2~3 it is small when, rGO/Fe must be contained3O4Mixed liquor；(3) it is kept stirring speed and bath temperature is constant, MnSO is added into gained mixed liquor4Solution, then rapidly joins again KMnO4With the mixed solution of KOH, when reaction 2~4 is small, obtain including rGO/Fe3O4/MnO2Mixed liquor；(4) rGO/Fe will be contained3O4/MnO2Mixed liquor repeated filtration, wash after in 140~160 DEG C of vacuum drying chambers heat at When reason 20~25 is small to obtain the final product.
- 2. preparation method according to claim 1, it is characterised in that graphene oxide quality and pure water body in step (1) Long-pending ratio is 1mg：1.5~2.0mL, oxygen content is 4.5~6.5% in graphene oxide, polyethylene glycol and graphene oxide Mass ratio is 5~10.
- 3. preparation method according to claim 1, it is characterised in that FeCl in step (2)2With the mass ratio of graphene oxide For 1/1~1.5/1；FeCl3With FeCl2Molar ratio is 2/1.
- 4. preparation method according to claim 1, it is characterised in that MnSO in step (3)4With FeCl2And FeCl3Gross mass Than for 0.6/1~0.75/1；KMnO4With MnSO4Mass ratio is 1/1.1~1/1.2；KOH and MnSO4And KMnO4Total mass ratio is 0.9/1~1/1.
- 5. preparation method according to claim 1, it is characterised in that ultrasonic time is 45~60min in step (1).
- 6. preparation method according to claim 1, it is characterised in that stir speed in step (2) in 20~40 DEG C of waters bath with thermostatic control Spend for 1400~1600rpm；Mixing speed is 2800~3200rpm in 70~80 DEG C of waters bath with thermostatic control.
- 7. preparation method according to claim 1, it is characterised in that ammonium hydroxide used is that the ammonium hydroxide of 25mg/mL is molten in step (2) Liquid.
- 8. preparation method according to claim 1, it is characterised in that water bath with thermostatic control temperature is 30 DEG C in step (1)；Step (2) in heating before for 30 DEG C, heating after be 75 DEG C.
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|---|---|---|---|---|
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306864A (en) * | 2008-06-25 | 2008-11-19 | 浙江工业大学 | Degradation process for environment estrogenic pollutant in water body |
| CN102120619A (en) * | 2011-01-11 | 2011-07-13 | 河北师范大学 | Preparation method of brain-coral-shaped birnessite type manganese dioxide |
| CN103285874A (en) * | 2013-06-13 | 2013-09-11 | 江苏中核华纬工程设计研究有限公司 | Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof |
| CN103693639A (en) * | 2013-12-13 | 2014-04-02 | 天津工业大学 | Preparation method of iron/manganese oxide doped graphene composite material |
| US20140377790A1 (en) * | 2013-06-19 | 2014-12-25 | Indian Institute Of Technology Madras | Metal nanoparticle decorated carbon nanotubes and methods of preparation and use |
| CN104888706A (en) * | 2015-06-08 | 2015-09-09 | 河海大学 | Magnetically separable compound adsorbent as well as preparation method and application thereof |
| CN105289493A (en) * | 2015-11-17 | 2016-02-03 | 辽宁大学 | Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof |
| CN106115796A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Preparation method of graphene-manganese dioxide nano material containing magnetic iron |
| CN106140090A (en) * | 2016-08-31 | 2016-11-23 | 南京尚易环保科技有限公司 | A kind of MnO for removing indoor formaldehyde2aCF material and preparation method thereof |
| CN106531472A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Preparation method of polypyrrole/graphene/ manganese oxide composite materials |
-
2017
- 2017-10-25 CN CN201711008658.7A patent/CN107913667B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306864A (en) * | 2008-06-25 | 2008-11-19 | 浙江工业大学 | Degradation process for environment estrogenic pollutant in water body |
| CN102120619A (en) * | 2011-01-11 | 2011-07-13 | 河北师范大学 | Preparation method of brain-coral-shaped birnessite type manganese dioxide |
| CN103285874A (en) * | 2013-06-13 | 2013-09-11 | 江苏中核华纬工程设计研究有限公司 | Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof |
| US20140377790A1 (en) * | 2013-06-19 | 2014-12-25 | Indian Institute Of Technology Madras | Metal nanoparticle decorated carbon nanotubes and methods of preparation and use |
| CN103693639A (en) * | 2013-12-13 | 2014-04-02 | 天津工业大学 | Preparation method of iron/manganese oxide doped graphene composite material |
| CN104888706A (en) * | 2015-06-08 | 2015-09-09 | 河海大学 | Magnetically separable compound adsorbent as well as preparation method and application thereof |
| CN105289493A (en) * | 2015-11-17 | 2016-02-03 | 辽宁大学 | Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof |
| CN106115796A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Preparation method of graphene-manganese dioxide nano material containing magnetic iron |
| CN106140090A (en) * | 2016-08-31 | 2016-11-23 | 南京尚易环保科技有限公司 | A kind of MnO for removing indoor formaldehyde2aCF material and preparation method thereof |
| CN106531472A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Preparation method of polypyrrole/graphene/ manganese oxide composite materials |
Non-Patent Citations (1)
| Title |
|---|
| XUBIAO LUO ET AL.: ""Adsorption of As (III) and As (V) from water using magnetite Fe3O4-reduced graphite oxide-MnO2 nanocomposites"", 《CHEMICAL ENGINEERING JOURNAL》 * |
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