CN109107531A - Remove the magnetic oxygenated graphene composite material and preparation method thereof of quadracycline in aqueous solution - Google Patents
Remove the magnetic oxygenated graphene composite material and preparation method thereof of quadracycline in aqueous solution Download PDFInfo
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
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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
- B01J20/28—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
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The present invention relates to a kind of magnetic oxygenated graphene composite materials and preparation method thereof of quadracycline in removal aqueous solution.Its main feature is that composition are as follows: by the graphene oxide and Fe of mass ratio 2:1-1:23O4Composition is blended in nanoparticle.It is an advantage of the present invention to provide a kind of more environmentally friendly, the preferable magnetic oxygenated graphene composite materials and preparation method thereof for removing quadracycline.The present invention is to be combined on graphene oxide that obtain a kind of magnetic oxygenated graphene composite material be adsorbent material using ferriferrous oxide nano particle, the material has higher Adsorption to the quadracycline in aqueous solution, the magnetic effect of material can guarantee that absorption and the aqueous solution of processing efficiently separate, and solve the problems, such as secondary pollution of the graphene oxide as adsorbent.
Description
Technical field
The present invention relates to a kind of magnetic oxygenated graphene composite material of quadracycline in removal aqueous solution and its preparations
Method.
Background technique
China is now annual about to produce more than 1300 kinds of medicinal chemicals, and wherein antibiotics drug annual output is up to 3.3 ten thousand tons.
Antibiotic is originally designed under low physiological dose generating biochemical activity in treatment terminal and then plays therapeutic purposes, however is permitted
More antibiotic at low concentrations simultaneously may be in conjunction with non-targeted receptor, and then generates various unpredictable physiological actions.This
The subtle effect of kind may gradually amplify over time by the continual input of antibiotic, finally even to wildlife
The ecosystem generates far-reaching and expendable influence.It is found in surface water, sewage, underground water and drinking water at present a variety of anti-
Raw element substance, these substances escape from water standard control mostly, and water treatment technology does not obviously dispel quite a few substance
Effect.Wherein tetracycline antibiotics are one of Chinese production at present and the maximum a kind of antibiotic of usage amount.Tetracyclines is anti-
Raw element is a kind of broad-spectrum antibiotic generated by actinomyces, is typical bactericidal properties drug, is usually used in pharmaceutical sector, animal husbandry and water
It produces in aquaculture, tetracycline antibiotics in use are not easy by animal metabolism and absorption, and antibiotic is often (female in an active
Body or metabolite) largely enter in water body.In addition, having also detected that a large amount of hydrochloric acid four in the waste water of pharmaceutical factory's discharge
Ring element class antibiotic, causes great harm the health of the ecosystem and the mankind.Therefore, quadracycline is controlled and reduces to exist
Residual in environment has caused environmental science circle or even the extensive concern of the public.
New material of the graphene oxide as carbon group element, since its high-specific surface area, high-ratio surface energy, high reaction are lived
Property makes it have excellent absorption property.Through it is various it is oxidizing after obtained graphene oxide, surface has a large amount of
Oxygen-containing functional group (such as hydroxyl, carboxyl, epoxy group), provides adsorption site abundant, and carboxyl and hydroxyl etc. are oxygen-containing
Functional group can generate hydrogen bond with water, improve the dissolubility of graphene oxide in water.Magnetic oxygenated graphene is to aoxidize
Improvement to a certain extent is carried out on the basis of graphene, it not only has the distinctive quantum size effect of nano material, small
Dimensional effect and skin effect etc. remain the good adsorption capacity of graphene oxide, more significantly have magnetism, are polluting
It is easy to separate from solution in object processing.
Summary of the invention
It is compound that an object of the present invention is to provide a kind of magnetic oxygenated graphene for removing quadracycline in aqueous solution
Material, the material have higher Adsorption to act on the quadracycline in aqueous solution, and the magnetic effect of the material can be with
Guarantee that absorption and the aqueous solution of processing efficiently separate the secondary pollution so as to avoid graphene oxide as adsorbent；
The second object of the present invention is to provide a kind of preparation method of above-mentioned composite material.
The magnetic oxygenated graphene composite material of quadracycline in a kind of removal aqueous solution, its special feature is that, group
Become: by the graphene oxide and Fe of mass ratio 2:1-1:23O4Composition is blended in nanoparticle.
The preparation method of the magnetic oxygenated graphene composite material of quadracycline in a kind of removal aqueous solution, especially it
It is in including the following steps:
(1) graphite powder is first passed through into pre-oxidation, obtains graphene oxide, drying for standby using oxidation；
(2) the graphene oxide ultrasound that step (1) obtains is removed as brown color graphene oxide colloidal solution；
(3) Fe is prepared using mixing coprecipitation3O4Nanoparticle is specifically weighed according to the mass ratio of 1:1-1:20
FeCl2·4H2O and FeCl3·6H2O adds water and stirs dissolution in container, while being slowly added to sodium hydroxide solution until solution
Become black, separated with 10000r/min high speed centrifugation, removal supernatant obtains dark thick product, does in 40 DEG C of baking ovens
It is dry spare；
(4) method by being blended, takes the graphene oxide and Fe of mass ratio 2:1-1:2 respectively3O4Nanoparticle, super
Graphene oxide and Fe under the conditions of sound3O4Nanoparticle distinguishes ultrasonic dissolution 2h, the graphite oxide then obtained with step (2)
The Fe that alkene colloidal solution and step (3) obtain3O4The solution of nanoparticle prepares magnetic oxygenated graphene composite material.
Further, include the following steps:
Step 1, graphene oxide is prepared based on improving Hummers method:
1) preoxidation process:
(1) three-neck flask for taking a 250mL sequentially adds the dense H of the 98% of 15mL2SO4, 2.5g K2S2O8、2.5g
P2O5, 90 DEG C are heated, stirring is allowed to be completely dissolved；
(2) graphite powder for adding 4g, is stirred to react 4h；
(3) reaction solution is slowly transferred in the beaker for filling 500mL deionized water along wall, is slowly poured out after standing
Clear liquid, precipitating, 50 DEG C are dried for standby to obtain pre-oxidation product；
2) process is reoxidized:
(1) three-neck flask for taking a 250mL is added 98% concentrated sulfuric acid of 36mL, sequentially adds 5g's under ice-water bath
The pre-oxidation product of potassium permanganate and 1g drying, then 35 DEG C of reaction 8h；
(2) reactant is poured slowly into the beaker for filling 500mL deionized water along wall, stirs and quality is added dropwise
The H that score is 30%2O2, until glassy yellow is presented in reactant, continue to stir 0.5h；
(3) it stands and pours out supernatant, washed to remove remaining ion with 10% hydrochloric acid solution, then use deionized water
Washing is repeatedly 7 up to solution to pH, is put in 50 DEG C of baking oven, obtained by drying to arrive graphene oxide；
Step 2, Fe is prepared using mixing coprecipitation3O4Nanoparticle:
(1) according to m (FeCl2·4H2O):m(FeCl3·6H2O)=0.5836:1 ratio weighs 1g FeCl2·4H2O,
0.5836g FeCl3·6H2O is sequentially placed into large beaker, and water 250mL is added to dissolve；
(2) be slowly added to while agitating 0.5moL/L sodium hydroxide solution until solution become black, then mend again
Add 1-2 drop 0.5moL/L sodium hydroxide solution above-mentioned, continues to stir 30min；
(3) reaction system stratification, upper layer are colourless liquids, and lower layer is dark solution, topple over removal supernatant liquid, will
Lower black solution deionized water and dehydrated alcohol wash 3 times respectively；
(4) the dark thick product that will be obtained, it is dry in 40 DEG C of vacuum ovens, it takes out stand-by；
Step 3, Fe prepared by the graphene oxide and step 2 prepared by the method for blending step 13O4Nanoparticle
Prepare at least one of magnetic oxygenated graphene of following three:
(1) according to m (Fe3O4): m (GO)=2:5 mass ratio weighs 0.2g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will
Magnetic oxygenated graphene is separated from solution, and 30 DEG C of dryings can obtain the first magnetic oxygenated graphene i.e. 2:5 magnetism oxygen
Graphite alkene.
(2) according to m (Fe3O4): m (GO)=5:5 mass ratio weighs 0.5g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will
Magnetic oxygenated graphene is separated from solution, and 30 DEG C of dryings can obtain second of magnetic oxygenated graphene i.e. 5:5 magnetism oxygen
Graphite alkene.
(3) according to m (Fe3O4): m (GO)=8:5 mass ratio weighs 0.8g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will
Magnetic oxygenated graphene is separated from solution, and it is magnetic that 30 DEG C of dryings can obtain the third magnetic oxygenated graphene abbreviation 8:5
Graphene oxide.
It is an advantage of the present invention to provide a kind of more environmentally friendly, the preferable magnetic oxygenated graphene for removing quadracycline is multiple
Condensation material and preparation method thereof.The present invention is to be combined on graphene oxide to obtain a kind of magnetic using ferriferrous oxide nano particle
Property graphene oxide composite material be adsorbent material, which has higher Adsorption to the quadracycline in aqueous solution, material
The magnetic effect of material can guarantee that absorption and the aqueous solution of processing efficiently separate, and solve two of graphene oxide as adsorbent
Secondary pollution problem.
Beneficial effects of the present invention are as follows:
1, the present invention is few using the graphene oxide number of plies of pre-oxidation system, and large specific surface area, preparation cost is cheap, operation letter
It is single.
2, the present invention prepares the technique of magnetic oxygenated graphene, and raw material is easy to get, and condition is easily-controllable, and the magnetic effect of material can be with
Guarantee that the aqueous solution of adsorption treatment efficiently separates adsorbent, prepares the novel environment friendly of quadracycline in efficient absorption aqueous solution
Adsorbent material.
3, it solves traditional handicraft and prepares many and diverse, the adsorbent material environmental protection technical problems such as easily separated, to hydrochloric acid in aqueous solution
Fourth Ring is known as higher absorption property.
Detailed description of the invention
Fig. 1 is the XRD of graphene oxide, and graphene oxide, which is 10.64 ° in 2 θ, nearby an apparent wider diffraction
Peak, i.e. graphene oxide diffraction maximum；
Fig. 2 is the XRD of magnetic oxygenated graphene, and when 2 θ are 10.64 °, there are a characteristic diffraction peak, this diffraction maximums
It is exactly the characteristic diffraction peak of graphene oxide, when 2 θ are 35.67 ° there is also a diffraction maximum, this diffraction maximum is Fe3O4It receives
The diffraction maximum of rice corpuscles (311) crystal face；
Fig. 3 is the hysteresis loop of magnetic oxygenated graphene, and magnetic saturation intensity is that 15.06emu/g illustrates magnetic coercive force almost
It is zero, shows that external magnetic field is removed, not the evidence of residual magnetization, therefore nanocomposite Fe3O4/ GO be superparamagnetic behavior and
High magnetic responsiveness；
Fig. 4 is the infrared of magnetic oxygenated graphene, wherein 3429cm-1,3195cm-1Broad peak be-OH stretching vibration institute
Cause, 1628cm-1Strong peak derive from the stretching vibration of C=O group, 1400cm-1,1092cm-1From C-O stretching vibration,
581cm-1Peak derives from Fe-O stretching vibration；
Fig. 5 is adsorption dynamics adsorption kinetics of the 1 magnetic oxygenated graphene (5:5) of application examples to quadracycline, with quasi- second motive force
Learn R when model is fitted2It is 0.9955, and the quasi- calculated equilibrium adsorption capacity of second order dynamic model is
126.9035mg/mL, closer to true experimental data, magnetic oxygenated graphene (5:5) meets the adsorption process of tetracycline
Quasi- second order dynamic model.Therefore illustrate that adsorption process belongs to chemical process, while also illustrate magnetic oxygenated graphene (5:
It 5) is adsorption to the absorption of tetracycline；
Fig. 6 is Adsorption thermodynamics of the 2 magnetic oxygenated graphene (5:5) of application examples to quadracycline, the line being fitted with L-type
Property related coefficient be 0.9977, Langmuir model be a kind of simulation ideally, be usually used in mono layer adsorption, so
Also illustrate that magnetic oxygenated graphene (5:5) belongs to the absorption of monolayer to the absorption of tetracycline simultaneously；
Fig. 7 be 3 magnetic oxygenated graphene (5:5) of application examples under condition of different pH to the adsorption effect of quadracycline,
There is a platform to the absorption of quadracycline in magnetic oxygenated graphene (5:5) when pH is 4.03~4.60, and works well,
Maximal absorptive capacity is up to 314mg/g, and when pH is 2.40~4.03, with the increase of pH, equilibrium adsorption capacity increases quickly；When pH exists
When 4.60~9.30, with the increase of pH, equilibrium adsorption capacity is reduced comparatively fast, when pH is greater than 9.30, with the increase of pH, equilibrium adsorption
There is a platform and reduces slow in amount.Reason may be that the isoelectric point bibliography of magnetic oxygenated graphene is about 3.5, when pH is small
When 3.5, magnetic oxygenated graphene is electropositive, and when pH is greater than 3.5, magnetic oxygenated graphene surface is elecrtonegativity.Hydrochloric acid four
When pH is less than 3.3, cation form accounts for mainly ring element, and pH mainly exists between 3.3 and 7.7 with amphoteric ion, and pH is greater than
When 7.7, first in the form of monovalence anion based on, when pH be greater than 9.7 when, based on dianions.Therefore in acid condition, band
Repulsive force between the magnetic oxygenated graphene and positively charged tetracycline of positive charge increases with the reduction of pH, also reduces
Suction-operated to positively charged tetracycline, on the contrary, under conditions of close to range between 3.3 and 7.7, tetracycline molecule
Amphoteric ion and negative charge density gradually increase, in pH=4.03~4.60, tetracycline and magnetic oxygenated graphene (5:5)
Between repulsive force it is relatively most weak, so the absorption to tetracycline is good.
Specific embodiment
Medium, is uniformly mixed using ultrasonic wave, is played to reunion by the method for magnetic oxygenated graphene preparation of the invention
Shear action, increasing specific surface area.Graphite powder is pre-oxidized, and the graphene oxide of high quality is prepared.It is proportionally added into oxygen
Graphite alkene and Fe3O4Nanoparticle.What is obtained is that a kind of can inhale the magnetic oxygenated graphene of quadracycline in adsorption aqueous solution
Attached dose.
The preparation method of the magnetic oxygenated graphene composite material of quadracycline in a kind of removal aqueous solution, specific implementation
Technical solution is as follows:
Graphene oxide (GO) is prepared based on improving Hummers method first, by 1-5g graphite powder by pre-oxidation, then
It is oxidized to graphene oxide, drying for standby, graphene oxide ultrasound removing is brown color graphene oxide colloidal solution.Secondly
Fe is prepared using mixing coprecipitation3O4Nanoparticle weighs FeCl according to 1:1-1:20 mass ratio2·4H2O and FeCl3·
6H2O adds water and stirs dissolution in large beaker, while being slowly added to sodium hydroxide solution until solution becomes black, product with from
The method of the heart carries out separation drying for standby.Finally by blending the method graphene oxide (GO) of mass ratio 2:1-1:2 and
Fe3O4Nanoparticle is prepared magnetic oxygenated graphene composite material and is characterized.It is inhaled with the magnetic oxygenated graphene (5:5) of preparation
Quadracycline is in attached water solution to simulate its absorption to quadracycline in waste water, and testing includes adsorption dynamics adsorption kinetics, absorption
The influence of thermodynamics and pH to adsorption process.
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1:
Step 1 is prepared graphene oxide (GO) based on improving Hummers method: the method prepares graphene oxide point
For two steps, i.e., preoxidation process and reoxidize process.
1) preoxidation process:
(1) three-neck flask for taking a clean and dry 250mL, sequentially add 15mL mass fraction be 98% it is dense
H2SO4, 2.5g K2S2O8, 2.5g P2O5, 90 DEG C are heated, stirring is allowed to be completely dissolved.
(2) graphite powder for adding 4g, is stirred to react 4h.
(3) reaction solution is slowly transferred in the beaker for filling 500mL deionized water along wall, stands 12h precipitating, slowly
Supernatant is poured out, is deposited in 50 DEG C of baking ovens and is dried for standby to obtain pre-oxidation product.
2) process is reoxidized:
(1) the dense sulphur that the mass fraction of 36mL is 98% is added in the three-neck flask for taking a clean and dry 250mL
Acid sequentially adds the potassium permanganate of 5g and the pre-oxidation product of 1g drying under ice-water bath, in 35 DEG C of reaction 8h.
(2) reactant is poured slowly into the beaker for filling 500mL deionized water along wall, stirs while matter is added dropwise
Measure the H that score is 30%2O2Glassy yellow is presented to reactant, continues to stir 0.5h.
(3) 12h is stood, solution layering, upper layer is colourless solution, and lower layer is golden yellow liquid, upper layer colourless solution is poured out,
It is multiple that the hydrochloric acid solution washing that 200mL mass fraction is 10% is added in golden yellow liquid, with 10000r/min high speed centrifugation
1moL/LBaCl is added until being centrifuged in obtained supernatant in 10min2Solution is generated without white precipitate, to remove remaining
Ion；
It is washed with deionized again repeatedly, with 10000r/min high speed centrifugation 10min, until the supernatant that centrifugation obtains is extremely
Neutral (pH 7) removes supernatant, and dark thick solid obtained by high speed centrifugation is put in 50 DEG C of baking oven, obtained by drying to arrive oxygen
Graphite alkene, characterization XRD such as Fig. 1.
Step 2 prepares Fe using mixing coprecipitation3O4Nanoparticle:
(1) according to m (FeCl2·4H2O):m(FeCl3·6H2O)=0.5836:1 ratio weighs 1g FeCl2·4H2O,
0.5836g FeCl3·6H2O is sequentially placed into large beaker, and water 250mL is added to dissolve.
(2) be slowly added to while agitating 0.5moL/L sodium hydroxide solution until solution become black, then mend again
The 0.5moL/L sodium hydroxide solution for adding 1-2d continues to stir 30min.
(3) the solution left standstill 4h that will be obtained, solution layering, upper layer is colourless liquid, and lower layer is dark solution, is then toppled over
Supernatant is removed, 200mL deionized water is added in dark solution and washs 3 times, is divided with 10000r/min high speed centrifugation 5min
From, upper layer is colourless liquid, and lower layer is dark thick solid, then dark thick solid is washed 3 times respectively with dehydrated alcohol,
It is separated with 10000r/min high speed centrifugation 5min, upper layer is colourless liquid, and lower layer is dark thick solid.
(4) the dark thick product for obtaining step (3), it is dry in 40 DEG C of vacuum ovens, it takes out stand-by.
Fe prepared by step 3, the graphene oxide (GO) prepared by the method for blending with step 1 and step 23O4Nanometer
Particle prepares three kinds of magnetic oxygenated graphenes:
(1) according to m (Fe3O4): m (GO)=2:5 mass ratio weighs 0.2g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasonic (40KHz) dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound (40KHz) 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, by magnetic
Property graphene oxide is separated from solution, and 30 DEG C of dryings can obtain the first magnetic oxygenated graphene abbreviation 2:5 magnetism oxygen
Graphite alkene.
(2) according to m (Fe3O4): m (GO)=5:5 mass ratio weighs 0.5g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasonic (40KHz) dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound (40KHz) 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, by magnetic
Property graphene oxide is separated from solution, and 30 DEG C of dryings can obtain second of magnetic oxygenated graphene abbreviation 5:5 magnetism oxygen
Graphite alkene.
(3) according to m (Fe3O4): m (GO)=8:5 mass ratio weighs 0.8g Fe respectively3O4With 0.5g graphene oxide
GO, by Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, graphene oxide
500mL deionized water is added in GO, ultrasonic (40KHz) dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed
It closes, then stirs 30min, then ultrasound (40KHz) 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, by magnetic
Property graphene oxide is separated from solution, and 30 DEG C of dryings can obtain the third magnetic oxygenated graphene abbreviation 8:5 magnetism oxygen
Graphite alkene.
Three kinds of magnetic oxygenated graphene characterization XRD such as Fig. 2, hysteresis loop such as Fig. 3, infrared such as Fig. 4.
Application example 1:
The magnetic oxygenated graphene of 0.0640g (5:5) plus water ultrasonic dissolution are weighed, being configured to concentration is 0.256mg/mL's
250mL solution.Then it weighs 0.0201g quadracycline and is configured to the 250mL solution that concentration is 0.0804mg/mL.Take 2mL magnetic
The quadracycline solution of property graphene oxide solution and 2mL are mixed in 5mL centrifuge tube, the temperature of water-bath constant temperature oscillator
25 DEG C are set as, these centrifuge tubes equipped with solution are then placed on water-bath constant temperature oscillator and carry out oscillation absorption, adsorption time
It is set as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h,
14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h.High speed centrifugation has been adsorbed, with syringe Aspirate supernatant, then
It is filtered with the water system filter membrane of 0.45um, arrives different adsorption time supernatants with ultraviolet specrophotometer measurement absorbance
The absorbance of quadracycline in liquid.If the magnetic oxygenated graphene of Fig. 5 (5:5) is to the adsorption dynamics adsorption kinetics of quadracycline.
Application example 2:
Prepare a series of concentration be respectively 0.05mg/mL, 0.1mg/mL, 0.15mg/mL, 0.2mg/mL, 0.25mg/mL,
The quadracycline solution of 0.3mg/mL, 0.35mg/mL take its 2mL and concentration for the magnetic oxygenated graphene of 0.2516mg/mL
(5:5) solution is mixed in equal volume, to be adsorbed that solution is centrifuged completely, and supernatant liquid filtering film is taken to survey absorbance.
If the magnetic oxygenated graphene of Fig. 6 (5:5) is to the Adsorption thermodynamics of quadracycline.
Application example 3:
It is molten with the magnetic oxygenated graphene (5:5) of hydrochloric acid tune 0.26mg/mL and the quadracycline of 0.0792mg/mL respectively
The pH value of liquid, pH value setting 1.38,2.40,4.03,4.60,6.33,6.98,8.36,9.30,9.52,10.84 respectively take 2mL same
Magnetic oxygenated graphene (5:5) solution of one pH value is mixed with quadracycline solution to be placed in constant temperature oscillator, and 23h is adsorbed,
Centrifuge separation takes out supernatant liquid filtering film and surveys absorbance.As the magnetic oxygenated graphene of Fig. 7 (5:5) under condition of different pH to salt
The adsorption effect of sour tetracycline.
Claims (3)
1. the magnetic oxygenated graphene composite material of quadracycline in a kind of removal aqueous solution, which is characterized in that composition are as follows: by
The graphene oxide and Fe of mass ratio 2:1-1:23O4Composition is blended in nanoparticle.
2. the preparation method of the magnetic oxygenated graphene composite material of quadracycline, feature exist in a kind of removal aqueous solution
In including the following steps:
(1) graphite powder is first passed through into pre-oxidation, obtains graphene oxide, drying for standby using oxidation；
(2) the graphene oxide ultrasound that step (1) obtains is removed as brown color graphene oxide colloidal solution；
(3) Fe is prepared using mixing coprecipitation3O4Nanoparticle is specifically weighed according to the mass ratio of 1:1-1:20
FeCl2·4H2O and FeCl3·6H2O adds water and stirs dissolution in container, while being slowly added to sodium hydroxide solution until solution
Become black, separated with 10000r/min high speed centrifugation, removal supernatant obtains dark thick product, does in 40 DEG C of baking ovens
It is dry spare；
(4) method by being blended, takes the graphene oxide and Fe of mass ratio 2:1-1:2 respectively3O4Nanoparticle, in ultrasonic item
Part lower graphene oxide and Fe3O4Nanoparticle distinguishes ultrasonic dissolution 2h, the graphene oxide glue then obtained with step (2)
The Fe that liquid solution and step (3) obtain3O4The solution of nanoparticle prepares magnetic oxygenated graphene composite material.
3. removing the preparation side of the magnetic oxygenated graphene composite material of quadracycline in aqueous solution as claimed in claim 2
Method, which comprises the steps of:
Step 1, graphene oxide is prepared based on improving Hummers method:
1) preoxidation process:
(1) three-neck flask for taking a 250mL sequentially adds the dense H of the 98% of 15mL2SO4, 2.5g K2S2O8, 2.5g
P2O5, 90 DEG C are heated, stirring is allowed to be completely dissolved；
(2) graphite powder for adding 4g, is stirred to react 4h；
(3) reaction solution is slowly transferred in the beaker for filling 500mL deionized water along wall, supernatant is slowly poured out after standing
Liquid, precipitating, 50 DEG C are dried for standby to obtain pre-oxidation product；
2) process is reoxidized:
(1) three-neck flask for taking a 250mL is added 98% concentrated sulfuric acid of 36mL, the Gao Meng of 5g is sequentially added under ice-water bath
The pre-oxidation product of sour potassium and 1g drying, then 35 DEG C of reaction 8h；
(2) reactant is poured slowly into the beaker for filling 500mL deionized water along wall, stirs and mass fraction is added dropwise
For 30% H2O2, until glassy yellow is presented in reactant, continue to stir 0.5h；
(3) it stands and pours out supernatant, washed to remove remaining ion with 10% hydrochloric acid solution, then be washed with deionized
Repeatedly until solution to pH be 7, be put in 50 DEG C of baking oven, it is obtained by drying arrive graphene oxide；
Step 2, Fe is prepared using mixing coprecipitation3O4Nanoparticle:
(1) according to m (FeCl2·4H2O):m(FeCl3·6H2O)=0.5836:1 ratio weighs 1gFeCl2·4H2O,
0.5836g FeCl3·6H2O is sequentially placed into large beaker, and water 250mL is added to dissolve；
(2) be slowly added to while agitating 0.5moL/L sodium hydroxide solution until solution become black, then add 1-2 again
0.5moL/L sodium hydroxide solution above-mentioned is dripped, continues to stir 30min；
(3) reaction system stratification, upper layer are colourless liquids, and lower layer is dark solution, removal supernatant liquid are toppled over, by lower layer
Dark solution deionized water and dehydrated alcohol wash 3 times respectively；
(4) the dark thick product that will be obtained, it is dry in 40 DEG C of vacuum ovens, it takes out stand-by；
Step 3, Fe prepared by the graphene oxide and step 2 prepared by the method for blending step 13O4Nanoparticle preparation
At least one of magnetic oxygenated graphene of following three out:
(1) according to m (Fe3O4): m (GO)=2:5 mass ratio weighs 0.2g Fe respectively3O4It, will with 0.5g graphene oxide GO
Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, in graphene oxide GO
500mL deionized water is added, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed, so
After stir 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will be magnetic
Graphene oxide is separated from solution, and 30 DEG C of dryings can obtain the first magnetic oxygenated stone of magnetic oxygenated graphene i.e. 2:5
Black alkene.
(2) according to m (Fe3O4): m (GO)=5:5 mass ratio weighs 0.5g Fe respectively3O4It, will with 0.5g graphene oxide GO
Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, in graphene oxide GO
500mL deionized water is added, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed, so
After stir 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will be magnetic
Graphene oxide is separated from solution, and 30 DEG C of dryings can obtain the magnetic oxygenated stone of the i.e. 5:5 of second of magnetic oxygenated graphene
Black alkene.
(3) according to m (Fe3O4): m (GO)=8:5 mass ratio weighs 0.8g Fe respectively3O4It, will with 0.5g graphene oxide GO
Fe3O4It is respectively placed in different beakers with graphene oxide GO, Fe3O4Middle addition 100mL deionized water, in graphene oxide GO
500mL deionized water is added, ultrasound 40KHz dissolves 4h respectively；To Fe3O4After GO all dissolution, two kinds of solution are mixed, so
After stir 30min, then ultrasound 40KHz time 2h；10min is centrifuged with the speed of 10000r/min with supercentrifuge, it will be magnetic
Graphene oxide is separated from solution, and it is magnetic oxygenated that 30 DEG C of dryings can obtain the third magnetic oxygenated graphene abbreviation 8:5
Graphene.
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