CN104098729B - The preparation method of a kind of magnetic oxygenated graphene molecules trace composite and application - Google Patents
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Abstract
The present invention relates to the preparation method of a kind of magnetic oxygenated graphene molecules trace composite (MGO-MIP) and application thereof, composite is with graphene oxide (GO) for carrier, at its finishing Fe3O4Magnetic components, and clofibric acid (CA) molecularly imprinted polymer is evenly distributed in magnetic oxygenated graphene sheet layer surface, formed and there is efficient and selective composite。The trace physical dimension of MGO-MIP, binding site and CA specificity coincide；The magnetic oxygenated graphene molecules trace composite preparation of the present invention is simple, convenient；Polymer beads is uniform, and specific surface area and pore volume are big, and the stereochemical structure of CA molecule is had special memory recognition function, the CA in water body is had to affinity and the selectivity of height；The present invention also compares with other adsorbing materials for the selective removal of CA in surface water, obtains better effect。
Description
Technical field
The present invention relates to the preparation method of a kind of magnetic oxygenated graphene molecules trace composite and application, the present invention relates to the removal technical research of CA in Different Waters in addition, if surface water, subsoil water, sewage, drinking water etc. are by the CA water body polluted。
Background technology
Medicine and personal care articles (PharmaceuticalandPersonalCareProducts, PPCPs) and metabolite thereof are constantly by draining or in the bathing entrance surrounding medium such as municipal sewage and soil。At present, Sewage Plant Inlet and outlet water, surface water, subsoil water and drinking water have been found that more than 50 kind of PPCPs material, at concentrations up to μ gL-1Level。Present situation that PPCPs is widely used and special physicochemical characteristic, bring certain potential risk to ecological environment and human health。
CA is most typical a kind of in PPCPs, is also that in current water system residue, activity is the strongest, report one of most commonly used medicine。CA in the North Sea and some lakes of Switzerland has been studied by Buser et al., and result shows that CA concentration in surface water environment has reached 1-2ngL-1。Stan and Heberer detect in the drinking water of Berlin CA at concentrations up to 165ngL-1。The research of subsoil water is shown by Heberer, and the tax in subsoil water of this material is deposited concentration and reached 7300ngL-1。CA has very strong polarity and very difficult biodegradation, existing research shows that the sewage treatment facility of routine cannot cut down such material, data in the Lausanne of Switzerland and More sewage treatment plant show that CA does not remove, and the monitoring result of CA in the sewage disposal system of Berlin is shown that clearance is almost nil by Heberer。Therefore how effectively to remove the CA of residual in water body and cause showing great attention to of research worker。
Graphene oxide contains substantial amounts of hydroxyl and carboxylic group and epoxy-functional, accordingly, it is capable to react with other compounds。During water processes, most of graphene composite material synthesizes all on this basis and applies。Graphene oxide is a kind of oxygen-containing abundant carbonaceous layered material, by the SP comprising hydroxyl3The carbon atom of hydridization, epoxy-functional and comprise the SP of carboxyl and carbonyl2The carbon atom composition of hydridization。Owing to graphene oxide can form hydrogen bond with aqueous solution, so stable colloidal dispersion can be formed in water。Cd(II removed by the graphene oxide sheet material such as GuixiaZhao from a large amount of water bodys) and Co(II), when PH6.0, T are 300K, maximal absorptive capacity is 106.3mgg respectively-1、68.2mgg-1。Wang Zhao etc., with graphene oxide and butyl titanate for raw material, utilize hydro-thermal method to be prepared for TiO2/ Graphene composite photocatalyst material, and with TiO2/ Graphene composite photocatalyst material is that organic dyestuff rhodamine B is carried out photocatalytic degradation by photocatalyst, the TiO that its photocatalytic activity is prepared under the same terms2。Zhangkai etc. apply Fe (OH)3Composite nano materials with graphene oxide synthesizes, effectively removes the arsenic in drinking water。When the concentration of Arsenic in Drinking Water is 51.14mgL-1Time, the clearance of arsenic has exceeded 95%, and maximum adsorption ability is 23.78mgg-1。Graphene oxide and composite applied research in water processes thereof remove the feasible approach provided of the CA in water body for it。
Molecularly imprinted polymer (Molecularlyimprintedpolymer, MIP), due to the identity of its uniqueness and selectivity, is that a water pollution with applications well prospect processes new technique。MIP being used for the control of CA, can improve the selectivity of removal, treatment effect also improves accordingly。17 beta-estradiol molecular engram polymers of the preparation such as LeNoir, are used successfully to selective absorption and remove trace 17 beta estradiol in water body, at 2 μ gL-1In the aqueous solution of object pollutant, the response rate of pollutant reaches (100 ± 0.6) %。The method synthesis of bisphenol A molecular engram granule of precipitation polymerisation such as LinYi, carry out the research of selective removal phenols estrogen from different source waters of bisphenol-A molecularly imprinted polymer, thus prove with a kind of typical compound for templated synthesis molecularly imprinted polymer, and remove the feasibility of similar compound in different water body with this polymer selective。The above research is carry out typical case's molecular engram evident characteristics of PPCPs, pollution amelioration and control technology in water body to provide scientific basis。
The present invention is with graphene oxide for carrier, and at its finishing Fe3O4Magnetic components, is evenly distributed in magnetic oxygenated graphene sheet layer surface by molecular engram, has synthesized the nano level magnetic oxygenated graphene molecules trace composite with high selectivity, absorbability and superparamagnetism。By studying this composite to the absorbability of CA and specific recognition capability, inquire into its feasibility of CA application in removing water body, thus providing strong theoretical foundation and technical support for the selective removal of CA in following actual environment water body。
Summary of the invention
The present invention is with graphene oxide plane for carrier, and at its finishing Fe3O4Magnetic components, molecular engram is evenly distributed in magnetic oxygenated graphene sheet layer surface the most at last, has synthesized the nano level magnetic oxygenated graphene molecules trace composite with high selectivity, absorbability and superparamagnetism。It is an object of the invention to provide the preparation method of the magnetic oxygenated graphene molecules trace composite of CA in a kind of efficient selective separation water body and application thereof。
The preparation method of the magnetic oxygenated graphene molecules trace composite that the present invention proposes, specifically comprises the following steps that
(1) synthesis of graphene oxide (GO): install 2000mL beaker in ice-water bath, is added slowly with stirring natural flake graphite (C) equipped with 150-250mL concentrated sulphuric acid (H2SO4) beaker in, maintain temperature at (0 ± 5) oC, be more successively slowly continuously added to 3-5g sodium nitrate (NaNO3) and 15-30g potassium permanganate (KMnO4) mixture, during addition control reaction temperature less than 15-25oC, KMnO4After addition, reaction temperature is warmed up to gradually 30-35oC, and in water bath with thermostatic control, stir 15-45min, slowly add people's 100-500mL deionized water again, temperature is made to gradually rise up to 70-100oC, after maintaining 10-20min at this temperature, with warm water, mixture is diluted to 1000-1500mL, pours 100-500mL30% hydrogen peroxide (H into2O2) solution, its objective is to remove remaining KMnO4, and by the gas produced, GO lamella is strutted, now solution can become glassy yellow from brown color gradually；Finally by solution centrifugal, and fully wash with dehydrated alcohol, 5%HC1 solution and deionized water and be centrifuged respectively, until sulfate radical-free ion in filtrate, in 50oC at the dry 48h of vacuum drying oven, sealing preservation stand-by；
(2) synthesis of magnetic oxygenated Graphene: graphene oxide powder 1.0-2.0g step (1) obtained is placed in round-bottomed flask, 150-300mL dimethylformamide (DMF) and water it is poured slowly in round-bottomed flask, ultrasonic 10-60min, makes GO be uniformly dispersed in DMF；Then 0.5-1.5gFe is added in the mixture3O4, mixture is warmed up to 140-155oC, the response time is 3-5h, heating rate 5 ~ 10oC/min condensing reflux, cools down after reaction, is separated by magnetic oxygenated Graphene with alnico magnets from liquid, and clean three times with deionized water, preserve stand-by in freeze dryer after dry 24h；
(3) synthesis of magnetic oxygenated graphene molecules trace composite: be dissolved in 20-130mL porogen by 0.1-1.2mmol template molecule, standby after ultrasonic 10-60min, the mixed solution obtained is pre-assembled solution；Reaction vessel adds magnetic oxygenated Graphene granule 0.1-10.0g, the oleic acid 1.0-10.0mL that step (2) obtains, after ultrasonic 5 ~ 20min, adds 1-10mmol cross-linking agent and pre-assembled solution, mix ultrasonic 5 ~ 60min。The mixed solution obtained is pre-polymer solution；In pre-polymer solution, add the porogen of 1.0-10.0g dispersant, 100-500mL, after mix homogeneously, add 0.1-1.0g initiator under ice bath state, in reactant liquor, pass into 5 ~ 20min nitrogen, remove oxygen in reactor, nitrogen state lower seal。Being placed in by reaction vessel in constant temperature rotating and culturing case, according to 0.2 ~ 0.5oC/min heating rate, be warming up to 45 ~ 83oC, and high speed rotating reacts 8 ~ 45h at such a temperature, forms magnetic oxygenated graphene molecules trace composite, described template molecule is clofibric acid；
(4) eluting of magnetic oxygenated graphene molecules trace composite: magnetic oxygenated graphene molecules trace composite is placed in the solvent of methanol and acetic acid composition and adopts soxhlet extraction to remove template molecule, the time of surname extraction is 10-120h, obtain MGO-MIP, wherein: the volume ratio of methanol and acetic acid is (1-10): (10-1)。
In the present invention, initiator described in step (3) is water soluble starter or oil-soluble initiator。
In the present invention, functional monomer described in step (3) be acrylic compounds or pyridines any one；Porogen is the mixed liquor of any one or two kinds of in acetonitrile, methanol, toluene, chloroform or carbon tetrachloride；Cross-linking agent is selected from trimethylol-propane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA), divinylbenzene-80(DVB-80), N, 0-bis-in acryloyl-L-phenylalaninol or pentaerythritol triacrylate (PETRA) any one。Most preferably from ethylene glycol dimethacrylate (EGDMA) or divinylbenzene-80(DVB-80)。
In the present invention, the dispersant described in step (3) is polyvinylpyrrolidone (PVP)。
In the present invention, the volume ratio of methanol described in step (4) and acetic acid is (7-9): (3-1), the time of surname extraction is 12-72h。
Utilize the magnetic oxygenated graphene molecules trace composite that preparation method of the present invention obtains for removing CA in water body。
The magnetic oxygenated graphene molecules trace composite that the inventive method prepares is utilized to separate for the efficient selective of trace medicine in water system。
The present invention also aims to utilize this material to remove the method for CA in water body。The method can be used for the Selective Separation of trace medicine in water system, and has sharp separation ability and higher selectivity, and capacity of resisting disturbance is strong, and the CA after enrichment can use organic solvent eluting。
Beneficial effects of the present invention:
The present invention is magnetic oxygenated graphene molecules trace composite, utilizes molecularly imprinted polymer that pollutant are separated by the specific surface area that the specific selectivity of template material and graphene oxide are huge from water body。The magnetic oxygenated graphene molecules trace composite of synthesis has good regeneration performance, this material Reusability repeatedly after trace ability there is not obvious decay yet, it is meant that magnetic oxygenated graphene molecules trace composite water process in technology application feasibility。Simultaneously this material solve conventional absorbtion material target contaminant is not optionally adsorbed and be difficult to from water body separate problem。
Accompanying drawing explanation
Scanning electron microscope (SEM) figure and transmission electron microscope (TEM) figure of Fig. 1 MGO-MIP, (a) scanning electron microscope (SEM) figure, (b) transmission electron microscope (TEM) figure。
Fig. 2 Fe3O4, MGO and MGO-MIP X-ray diffraction (XRD) figure。
Fig. 3 Fe3O4, MGO and MGO-MIP hysteresis curve。
The selectivity experiment of Fig. 4 MGO-MIP。
Detailed description of the invention
Below in conjunction with embodiment, the present invention done further detailed description, but embodiments of the present invention are not limited to this。
Embodiment 1
The synthetic method of MGO-MIP of the present invention is as follows:
(1) synthesis of graphene oxide (GO): install beaker (2000mL) in ice-water bath, is added slowly with stirring 10g natural flake graphite (C) equipped with 230mL concentrated sulphuric acid (H2SO4) beaker in, maintain temperature at 0oC, be more successively slowly continuously added to 5.0g sodium nitrate (NaNO3) and 30.0g potassium permanganate (KMnO4), control reaction temperature during addition less than 20oC, KMnO4After addition, reaction temperature is warmed up to gradually 35oC, and in water bath with thermostatic control, stirs 30min, it is slow added into 460mL deionized water, and makes temperature gradually rise up to 98oC, after maintaining 15min at this temperature, with warm water 1400mL, mixture is diluted, pour 30% hydrogen peroxide (H into2O2) solution, its objective is to remove remaining KMnO4, and by the gas produced, GO lamella is strutted, now solution can become glassy yellow from brown color gradually；Finally by solution centrifugal, and fully wash with dehydrated alcohol, 5%HC1 solution and deionized water and be centrifuged respectively, until sulfate radical-free ion in filtrate, in 50oC at the dry 48h of vacuum drying oven, sealing preservation stand-by。
(2) synthesis of magnetic oxygenated Graphene: graphene oxide powder 2.0g step (1) obtained is placed in round-bottomed flask, 200mL dimethylformamide (DMF) and water it is poured slowly in round-bottomed flask, ultrasonic 30min, makes GO be uniformly dispersed in DMF；Then 0.98gFe is added in the mixture3O4, mixture is warmed up to 152oC, so as to seethe with excitement, condensing reflux 4h, cool down after reaction, with alnico magnets, magnetic oxygenated Graphene is separated from liquid, and clean three times with deionized water, preserve stand-by in freeze dryer after dry 24h。
(3) synthesis of magnetic oxygenated graphene molecules trace composite: be dissolved in by 1.92mmolCA in 10mL acetonitrile/toluene (75/25, v/v), standby after ultrasonic 30min, the mixed solution obtained is pre-assembled solution；Reaction vessel adds magnetic oxygenated Graphene granule 0.3g, the oleic acid 3.0mL that step (2) obtains, after ultrasonic 15min, adds cross-linking agent DVB-805.46mL and pre-assembled solution, mix ultrasonic 30min。The mixed solution obtained is pre-polymer solution；In pre-polymer solution, add PVP1.2g, acetonitrile/toluene (75/25, v/v) 200mL, after mix homogeneously, add AIBN0.28g under ice bath state, in reactant liquor, pass into 10min nitrogen, remove oxygen in reactor, nitrogen state lower seal。Being placed in by reaction vessel in constant temperature rotating and culturing case, be warming up to 65oC, and high speed rotating reacts 24h at such a temperature, forms magnetic oxygenated graphene molecules trace composite, described template molecule is clofibric acid；
(4) eluting of magnetic oxygenated graphene molecules trace composite: MGO-MIP is placed in the solvent of methanol and acetic acid composition and adopts soxhlet extraction to remove template molecule, the time of surname extraction is 48h, obtain MGO-MIP, wherein: the volume ratio of methanol and acetic acid is 9:1。
The magnetic oxygenated graphene molecules trace composite of synthesis is carried out indices experiment:
The configuration of surface of magnetic oxygenated graphene molecules trace composite is characterized:
The spherical little granule as it is shown in figure 1, MGO-MIP is creamy white, smooth surface, uniform particle sizes, and it is evenly distributed in graphene oxide lamella surface。
As in figure 2 it is shown, Fe3O4The diffraction spectral peak of nanoparticle occurs in 2 θ=30.2,35.5,43.1,53.4,57.0 and 62.6 places, with standard Fe3O4Characteristic diffraction peak match, and MGO, MGO-MIP and Fe3O4There is identical characteristic peak, it was shown that Fe3O4Nanoparticle is wrapped by the composite。
As it is shown on figure 3, MGO and the MGO-MIP granule prepared is along with the increase of externally-applied magnetic field, intensity of magnetization increase, after externally-applied magnetic field increases to certain value, the intensity of magnetization reaches capacity, its saturation magnetization respectively 25.6 and 23.4emug-1。And B-H loop was the Hypothesis of Single Curve Build Up of initial point, illustrate that sample has good superparamagnetism。
The magnetic oxygenated graphene molecules trace composite of synthesis is carried out absorption property index characterization:
1) accurately weigh the some parts of 5mgMGO-MIP, be placed in 30mL tool plug vial, be separately added into 0～1500mgL-1CA aqueous solution 5mL, static adsorption a period of time in constant temperature oscillator, carries out Scatchard matching, can be calculated the maximum apparent binding capacity Q of specific binding sitemax1Respectively 170mgg-1。
2) being respectively charged into by 5mgMGO-MIP in the tool plug vial of 30mL, being then respectively adding 5mL concentration is 100mgL-1CA aqueous solution, the binding kinetics character of Study Polymer Melts。After experiment proves 30min, absorption substantially achieves balance。
3) weigh 5mgMGO-MIP to be placed in the tool plug vial of 30mL, be then respectively adding 5mL, 10-100mgL-1CA/CBZ mixed liquor。With the velocity fluctuation 2h of 200rpm on 25oC constant temperature oscillator after sealing, then reaction bulb is taken out in timing, studies the MGO-MIP specific selectivity to CA。Result shows that the MGO-MIP absorption property to CA is far above CBZ, it was demonstrated that MGO-MIP itself exists the specificitys such as the obligate bonding reaction of the memory hole of fixed size and shape, binding site, template molecule and binding site。
4) weighing 10mgMGO-MIP, before reusing, in methanol/acetic acid (9/1, v/v) mixed liquor, ultrasonic extraction for several times, can't detect CA until in filtrate every time, then again with methanol drip washing, and vacuum drying carries out the Study on reuse of MGO-MIP。After result proves this magnetic oxygenated graphene molecules trace composite Reusability 8 times, trace ability also decays。
Embodiment 2
The application of surface water mark-on CA removed by the magnetic oxygenated graphene molecules trace composite of the present invention: surface water water sample takes from Water of Huangpu River, and water sample is before use with 0.45 μm of membrane filtration。The dilution of surface water water sample deionized water is obtained a series of water sample, a series of concentration of CA mark-on in all water samples。5.0mL difference surface water water sample is placed in the 30mL tool plug vial containing 5mgMGO-MIP, with the velocity fluctuation 2h of 200rpm on 25oC constant temperature oscillator after sealing, then reaction bulb is taken out in timing, filtering with connecing microporous filter membrane (Φ=0.45 μm) under 2mL syringe, in filtrate, the free concentration HPLC of CA measures。The removal that the MGO-MIP of synthesis is used in surface water CA by this research, have evaluated MGO-MIP for the feasibility of CA in obligate removal polluted water body。
Claims (7)
1. the preparation method of a magnetic oxygenated graphene molecules trace composite, it is characterised in that specifically comprise the following steps that
(1) synthesis of graphene oxide GO: install 2000mL beaker in ice-water bath, natural flake graphite is added slowly with stirring in the beaker equipped with 150-250mL concentrated sulphuric acid, maintain temperature at (0 ± 5) oC, successively slowly it is continuously added to the mixture of 3-5g sodium nitrate and 15-30g potassium permanganate again, reaction temperature is controlled less than 15-25oC, KMnO during addition4After addition, reaction temperature is warmed up to gradually 30-35oC, and in water bath with thermostatic control, stir 15-45min, it is slow added into 100-500mL deionized water, makes temperature gradually rise up to 70-100oC, after maintaining 10-20min at this temperature, with warm water, mixture is diluted to 1000-1500mL, pours 100-500mL30% hydrogenperoxide steam generator into, its objective is to remove remaining potassium permanganate, and by the gas produced, GO lamella is strutted, now solution can become glassy yellow from brown color gradually；Finally by solution centrifugal, and fully wash with dehydrated alcohol, 5%HC1 solution and deionized water and be centrifuged respectively, until sulfate radical-free ion in filtrate, in 50oC at the dry 48h of vacuum drying oven, sealing preservation stand-by；
(2) synthesis of magnetic oxygenated Graphene: graphene oxide powder 1.0-2.0g step (1) obtained is placed in round-bottomed flask, 150-300mL dimethylformamide and water it is poured slowly in round-bottomed flask, ultrasonic 10-60min, makes GO be uniformly dispersed in dimethylformamide；Then 0.5-1.5gFe is added in the mixture3O4, mixture is warmed up to 140-155oC, the response time is 3-5h, heating rate 5 ~ 10oC/min condensing reflux, cools down after reaction, is separated by magnetic oxygenated Graphene with alnico magnets from liquid, and clean three times with deionized water, preserve stand-by in freeze dryer after dry 24h；
(3) synthesis of magnetic oxygenated graphene molecules trace composite: be dissolved in 20-130mL porogen by 0.1-1.2mmol template molecule, standby after ultrasonic 10-60min, the mixed solution obtained is pre-assembled solution；Reaction vessel adds magnetic oxygenated Graphene granule 0.1-10.0g, the oleic acid 1.0-10.0mL that step (2) obtains, after ultrasonic 5 ~ 20min, adds 1-10mmol cross-linking agent and pre-assembled solution, mix ultrasonic 5 ~ 60min；The mixed solution obtained is pre-polymer solution；In pre-polymer solution, add the porogen of 1.0-10.0g dispersant, 100-500mL, after mix homogeneously, add 0.1-1.0g initiator under ice bath state, in reactant liquor, pass into 5 ~ 20min nitrogen, remove oxygen in reactor, nitrogen state lower seal；Being placed in by reaction vessel in constant temperature rotating and culturing case, according to 0.2 ~ 0.5oC/min heating rate, be warming up to 45 ~ 83oC, and high speed rotating reacts 8 ~ 45h at such a temperature, forms magnetic oxygenated graphene molecules trace composite, described template molecule is clofibric acid；
(4) eluting of magnetic oxygenated graphene molecules trace composite: magnetic oxygenated graphene molecules trace composite is placed in the solvent of methanol and acetic acid composition and adopts soxhlet extraction to remove template molecule, the time of surname extraction is 10-120h, obtain MGO-MIP, wherein: the volume ratio of methanol and acetic acid is (1-10): (10-1)。
2. preparation method according to claim 1, it is characterised in that initiator described in step (3) is water soluble starter or oil-soluble initiator。
3. preparation method according to claim 1, it is characterised in that porogen described in step (3) is the mixed liquor of any one or two kinds of in acetonitrile, methanol, toluene, chloroform or carbon tetrachloride；Cross-linking agent selected from trimethylol-propane trimethacrylate, ethylene glycol dimethacrylate, divinylbenzene-80, N, O-bis-in acryloyl-L-phenylalaninol or pentaerythritol triacrylate any one。
4. preparation method according to claim 1, it is characterised in that the dispersant described in step (3) is polyvinylpyrrolidone。
5. preparation method according to claim 1, it is characterised in that the volume ratio of methanol described in step (4) and acetic acid is (7-9): (3-1), the time of surname extraction is 12-72h。
6. the magnetic oxygenated graphene molecules trace composite that a preparation method as claimed in claim 1 obtains, it is characterised in that be used for removing clofibric acid in water body。
7. the magnetic oxygenated graphene molecules trace composite that a preparation method as claimed in claim 1 obtains, it is characterised in that for the Selective Separation of trace medicine in water system。
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| CN105148876A (en) * | 2015-09-06 | 2015-12-16 | 江南大学 | Preparation method for surface molecular imprinting nano-composite material of magnetic graphene |
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| CN109092254B (en) * | 2018-08-16 | 2021-09-21 | 广东工业大学 | Preparation and application method of double-virtual-template phthalate molecularly imprinted magnetic material |
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