CN110252251A - Porous composite adsorbing material of a kind of magnetism 3D and preparation method thereof - Google Patents

Porous composite adsorbing material of a kind of magnetism 3D and preparation method thereof Download PDF

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CN110252251A
CN110252251A CN201910471032.2A CN201910471032A CN110252251A CN 110252251 A CN110252251 A CN 110252251A CN 201910471032 A CN201910471032 A CN 201910471032A CN 110252251 A CN110252251 A CN 110252251A
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porous composite
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CN110252251B (en
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刘亚敏
邹沛琳
赵基甫
喻晓静
陈艺兰
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Fujian University of Technology
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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Abstract

The invention discloses porous composite adsorbing material of a kind of magnetism 3D and preparation method thereof, this adsorbent material uses graphene oxide, FeCl3/FeSO4And polymerization amine compound is raw material, magnetic porous solid absorbent is made under ultrasonic disperse effect, this adsorbent material internal gutter spatially interworking architecture is conducive to the quick progress of adsorption/desorption so that adsorption/desorption diffusional resistance reduces.The material remains the intrinsic high surface area characteristic of graphene oxide, and there are a large amount of basic groups, and adsorbent material to be made to have larger enhancing to the adsorptive selectivity and adsorbance of the substances such as sour gas between simultaneous oxidation graphene layer.Ferromagnetism nano material Fe3O4It is compound be quickly for recycling and reuse using the magnetic characteristic of material so that this solid adsorption material can be convenient.

Description

Porous composite adsorbing material of a kind of magnetism 3D and preparation method thereof
Technical field
The present invention relates to adsorbent material fields, especially porous composite adsorbing material of a kind of magnetism 3D and preparation method thereof.
Background technique
In recent years, have superhigh specific surface area (theoretical value has reached 2630m2/ g) graphene-based serial nano material draw Play extensive concern in the world.Graphene-based material is a kind of two-dimensional surface material, with its huge specific surface area, good machine Tool performance, thermal conductivity etc. are widely used in the row such as anti-skidding fuel cell, material modification, antirust, sea water desalination, war industry Industry, such as it is used as battery electrode material, semiconductor devices, transparent display screen, sensor, capacitor raw material, in these applications Except, the huge specific surface area performance that graphene-based material is shown makes it have the potential quality as good adsorption material, but It is this huge specific surface area of graphene-based material only when it when two-dimensional plane state just to show, when multiple single layers When graphene-based material exists simultaneously, due to the effect of the huge Van der Waals force of its interplanar, graphene-based material is with agglomerate Existing for particle form, this aggregate similar to particulate carbon-graphite piece results in grapheme material and loses two dimension originally Characteristic, so that its specific surface area actively declines.Therefore, only overcome gravitation between two-dimensional surface and construct three-dimensional grapheme substrate Material could enable graphene-based material to be more preferably applied to adsorption process.
In addition, generally for regenerating and reusing adsorbent material, the adsorbent of saturation absorption pollutant must used It is smoothly detached out from mixture afterwards.And for nano adsorber, recycling is a huge challenge, because due to receiving The characteristic of small particle and lightweight is often presented in rice adsorbent, extremely difficult with the separation of mixture after saturation absorption.Meanwhile Once these nano-sized particles enter external environment, it is likely that pose a threat to human health.In recent years, Magneto separate is answered With, i.e., can be by simple Magneto separate from anti-if adsorbent material has magnetism so that this problem knows about the road Jue Zhi Answer the adsorbent that adsorption saturation is effectively collected in mixture.But most of adsorbent material does not have magnetism, it is therefore desirable to It prepares and has magnetic composite Nano adsorbent material.Iron (Fe), nickel (Ni) or cobalt (Co) often as magnetic material application, Middle iron-based material is a kind of material that magnetic property is excellent, and has natural abundance high, and at low cost, chemical component is simple, environment friend The advantages that good, may prepare the composite magnetic adsorption material for having excellent magnetic if it is compound with other materials progress Material.
Wang et al.[1]Fe is improved by introducing acrylate (PDDA)3O4Performance, which increase the surface areas of adsorbent And reduce its crystalline size.However, nanometer Fe3O4Particle is easy to form aggregate, the significant shadow of the aggregation of particle in aqueous solution It rings their surface characteristic and reduces their absorption property.In addition, Fe3O4It is easy to undergo phase transition by oxidation reaction.Sun etc. People[2]ZrO is prepared using one-step synthesis method method2- Fe3O4Composite material, by Fe3O4Nanoparticle and another metal oxide knot Altogether, the aggregation of nanoparticle is prevented.Yao et al.[3]Fe is prepared by thermosoling3O4/ graphene composite material, with improve from Dyestuff is removed in aqueous solution.Vu et al.[4]Fe is added in GO by being co-precipitated3O4In nano particle, gained compound adsorbent can be same When As(V is removed from mixed system) and Cr(VI).
Citation
[1] T. Wang, L. Zhang, H. Wang, et al., Controllable synthesis of hierarchical porous Fe3O4 particles mediated by poly(diallyldimethylammonium chloride) and their application in arsenic removal, Appl. Mater. Interfaces. 5 (2013) 12449–12459.
[2] T. Sun, Z. Zhao, Z. Liang, et al., Efficient removal of arsenite through photocatalytic oxidation and adsorption by ZrO2-Fe3O4 magnetic nanoparticles. Appl. Surf. Sci. 416 (2017) 656–665.
[3] Y. Yao, S. Miao, S. Liu, et al., Synthesis, characterization, and adsorption properties of magnetic Fe3O4@graphene nanocomposite, Chem. Eng. J. 184(2012) 326–332.
[4] H.C. Vu, A.D. Dwivedi, T.T. Le, et al., Magnetite graphene oxide encapsulated in alginate beads for enhanced adsorption of Cr(VI) and As(V) from aqueous solutions: Role of crosslinking metal cations in pH control, Chem. Eng. J. 307(2016) 220–229.
As previously mentioned, the magnetic composite constructed by present, often with magnetic Nano material Fe3O4Based on, by drawing Enter other materials, such as acrylate, metal oxide agent graphene, Lai Gaishan magnetic Nano material Fe3O4Performance, The increase of adsorbent material specific surface area, the increase of adsorption capacity are limited, and constructed composite material, which mainly passes through, to be overcome Strong particles' interaction between magnetic nanoparticle and the behavior for reducing particle aggregation, ensure that itself accordingly Active surface does not reduce.Therefore this composite material does not break through Fe3O4Itself specific surface area characteristic, also fails to give full play to Composite material reapective features, prevent the advantages of material prepared is from taking into account raw material.
Summary of the invention
The case where for the prior art, the purpose of the present invention is to provide one kind to have Fe3O4Material it is magnetic same When, the huge specific surface area feature of graphene oxide composite material is maintained, and the activity for increasing adsorbent material inner surfaces of pores is inhaled Porous composite adsorbing material of magnetic 3D of attachment position and preparation method thereof.
In order to realize above-mentioned technical purpose, the technical solution adopted by the present invention are as follows:
A kind of preparation method of the porous composite adsorbing material of magnetism 3D comprising following steps:
(1) it disperses graphene oxide in 40~60 ml deionized waters and ultrasonic disperse handles 15~20 min and concentration is made For the graphene oxide solution of 0.3~0.6mg/ml, then it is slow added into sub- by the four water sulfuric acid that concentration is 5~7 mg/ml The mixed solution that the ferric chloride (FeCl36H2O) that iron and concentration are 10~12 mg/ml is mixedly configured into, solution to be mixed are all added Afterwards, mixed system is ultrasonically treated 20 min, is then stirred for handling, be warming up to mixed system temperature during stir process 40~50 DEG C, when temperature is warming up to preset temperature, sodium hydroxide solution is instilled into mixed system, make its pH value to 10 with On, it is then warming up to 80~90 DEG C again and continues 30~60 min of stir process, is then cooled to room temperature, after standing cooling, The sediment being centrifugated out in mixed system, and after being washed with deionized processing at least 3 times, place it in 90 DEG C true It is dried under Altitude, the product Fe@GO of acquisition；
(2) product Fe@GO obtained is mixed with triethly orthoacetate by the solid-to-liquid ratio of 0.4~0.6ml/mg, then at ultrasound Reason makes product Fe@GO is completely homogeneous to be scattered in triethly orthoacetate, then adds again by p-methyl benzenesulfonic acid and product Fe@GO Mass ratio is that p-methyl benzenesulfonic acid is added in mixed solution by the ratio of 0.02~0.04 mg/mg, and is placed in water in mixed solution In thermal response kettle, 36~48 h of reaction treatment is carried out with 130 DEG C of condition, after the reaction was completed, by sodium hydroxide solution and product Fe@GO addition is than being that the sodium hydroxide solution that concentration is 1 mol/L is added in the ratio of 0.4~0.6 ml/mg, and is vigorously stirred place Manage 4 h, it is after the completion of stirring, mixed system is completely cooling, then be centrifugated out sediment and repeat deionized water washing and from The heart separates at least 2 times, then with acetone washing at least 2 times and is centrifugated out sediment, finally, the sediment isolated is placed in Vacuum drying treatment under room temperature obtains product Fe@GO- ester；
(3) under nitrogen atmosphere, it disperses product Fe@GO- ester in Isosorbide-5-Nitrae-dioxane in the ratio of 5~8 mg/ml, then N,N-Dimethylformamide is instilled in 1 drop/1O ml ratio, 20 min of ultrasonic treatment is then carried out, then presses product Fe@again Oxalyl chloride is added than the ratio for being 3 ml/mg in the addition of GO- ester and oxalyl chloride, and continues to be stirred to react place under nitrogen atmosphere Reason, after complete reaction, the solid content in mixed solution is centrifugated out, and disperse solid content in the ratio of 2 mg/ml It in methylene chloride, is stirred for and is ultrasonically treated 10 min, then again isolate the solid content in solution, and press 2~4 The dispersion concentration ratio of mg/ml is scattered in Isosorbide-5-Nitrae-dioxane, and 20~30 min are then ultrasonically treated, and presses product later Fe GO- ester: polyamine based compound=1: polyamine based compound is added in 10 ratio, then proceedes to 6 h of ultrasonic treatment, then exists It under the conditions of 373 K, is placed in nitrogen atmosphere and is stirred to react, after system reaction to be mixed is completed and cooled down, be centrifugated out solid Then object is scattered in Isosorbide-5-Nitrae-dioxane in the dispersion concentration ratio of 5~10 mg/ml, and be ultrasonically treated 10 min, Ultrasound is completed and after mixed system cooling, is centrifugated out solid content and repeats deionized water washing and centrifuge separation at least 2 times, With acetone washing at least 2 times and solid content is isolated again, disperses deionization in the dispersion concentration ratio of 5~10 mg/ml for it In water, then after 24 h of vacuum drying treatment, solids separation is gone out, obtains the porous composite adsorbing material of magnetic 3D.
Further, graphene oxide as described in step (1) is commercial graphene.
Further, four aqueous ferrous sulfates and concentration that concentration is 5~7 mg/ml in step (1) are 10~12 mg/ml The volume ratio of mixed solution and deionized water that ferric chloride (FeCl36H2O) is mixedly configured into is 100: 40~60.
Further, the polyamine based compound in step (3) is polyethyleneimine or polyamine group ionic liquid.
The advantages of above scheme, is:
(1) present invention is to use graphene oxide, FeCl3/FeSO4And polymerization amine compound is raw material, using ultrasonic wave plus The strong dispersion degree of each component and the conjugation of functional group, so that magnetic three-dimensional porosu solid sorbent material be made.
(2) sorbent material of the present invention is by forming Fe on two dimensional oxidation graphene surface functional group3O4And had There is the solid material compared with ferromagnetism function.
(3) present invention resets principle using Johnson-Claisen ortho-acetate and turns hydroxyl group existing for the surface GO Become carboxylic group, increases the carboxylic group on the surface GO.
(4) present invention utilizes the form of chemical bonds, the characteristics of using amido easily in conjunction with carboxyl, between multilayer GO It is inserted into polyamine based compound, the interlayer polymerization for avoiding GO has been formed simultaneously having using polyamine based compound as interlayer support object The three-dimensional material in three-dimensional intercommunication duct.
A kind of porous composite adsorbing material of magnetism 3D, is made by preparation method described above.
Using above-mentioned technical solution, compared with prior art, the present invention it has the beneficial effect that use of the present invention Graphene oxide, FeCl3/FeSO4And polymerization amine compound is raw material, under ultrasonic disperse booster action, first with chemistry Modification method decorates Fe in surface of graphene oxide3O4, Fe is secured in substrate3O4Nano particle simultaneously reduces nano particle Aggregation, while material being made to have good magnetism.The amido of polyamine based compound and surface of graphene oxide carboxylic are utilized later The combination of base group overcomes the reunion of graphene oxide interlayer so that polyamine based compound is inserted into graphene oxide interlayer, and The 3-dimensional multi-layered solid material for having intercommunication duct has been made.Therefore, final prepared magnetic porous solid absorbent, is having Standby Fe3O4Graphene oxide composite material huge specific surface area feature is maintained while the magnetism of material, and due to interlayer polyamines base The presence of compound increases the activated adoption point (amido) of adsorbent material inner surfaces of pores.To improve the choosing of absorption Selecting property and adsorption capacity are especially improved to gas (such as sour gas, CO2Deng) and heavy metal ion etc. adsorption effect.
Detailed description of the invention
The present invention program is further elaborated with reference to the accompanying drawings and detailed description:
Fig. 1 is the porous composite adsorbing material FTIR result figure of magnetic 3D of the present invention program embodiment；
Fig. 2 is the porous composite adsorbing material graph of pore diameter distribution of magnetic 3D of the present invention program embodiment；
Fig. 3 is the porous composite adsorbing material TGA result figure of magnetic 3D of the present invention program embodiment.
Specific embodiment
Embodiment
A kind of preparation method of the porous composite adsorbing material of magnetism 3D comprising following steps:
(1) it chooses commercial oxidation graphene 30mg to be scattered in 50ml deionized water, is ultrasonically treated 20min, delay after being completely dispersed The slow mixed solution that 100ml is added and is mixedly configured by four aqueous ferrous sulfates (600mg) and ferric chloride (FeCl36H2O) (1000mg), so After being ultrasonically treated 20min afterwards, mixed system is heated to 40oC, then instill few drops of sodium hydroxide solutions while stirring, adjusts it PH to 10 is continuously heating to 80 oC, is cooled to room temperature after stirring 30min, after being centrifugated out sediment, deionized water washing It is dried in vacuum overnight under 90 oC after three times, the sample after drying is placed in sample bottle stand-by (labeled as Fe@GO).
(2) it takes in 130mg Fe@GO sample merging beaker, and 50ml triethly orthoacetate is added, be ultrasonically treated about 30min 3mg p-methyl benzenesulfonic acid is added afterwards, mixed solution, which is placed in hydrothermal reaction kettle, reacts 40h under the conditions of 403K, be added 50ml's later The potassium hydroxide solution of 1mol/L is vigorously stirred about 4h, completely after cooling, is centrifugated out sediment and repeats deionized water and wash It washs and is centrifugated 2 times, then with acetone washing 2 times and be centrifugated, final sample at room temperature, is dried in vacuum overnight, sample (it is labeled as Fe@GO- ester) for use.
(3) the Fe@GO- ester sample of 25mg is taken, is scattered in Isosorbide-5-Nitrae-dioxane of 5ml under nitrogen atmosphere, and instills 1 drop N,N-Dimethylformamide (DMF) is ultrasonically treated 20min, the oxalyl chloride of 75ml is then added dropwise, later under nitrogen atmosphere It is stirred overnight.Then sample solution completely after reaction is dispersed separated solid matter out in sample is centrifugated out In 15 ml methylene chloride, 10min is stirred and be ultrasonically treated, is then centrifuged in the solid matter isolated merging beaker, and be added Isosorbide-5-Nitrae-dioxane of 15 ml, be ultrasonically treated 20min after be added 250mg polyethyleneimine, be ultrasonically treated 6h, then 373K, It is stirred overnight in nitrogen atmosphere.It is centrifugated out solid content after cooling, is then scattered in Isosorbide-5-Nitrae-dioxane of 50ml, It is ultrasonically treated 10min, centrifuge separation after being repeated 2 times, after continuing to use acetone cleaning 2 times, is scattered in 25ml deionized water In, rear obtained solid is the porous composite adsorbing material of magnetism 3D to vacuum freeze drying for 24 hours.
Characterization of The Products test
For the architectural characteristic for studying the porous composite adsorbing material of prepared magnetism 3D, (FTIR points of surface functional groups analysis is done to it Analysis), thermal stability analysis (TGA) and specific surface area, pore analysis (BET analysis).Fig. 1 is that the present embodiment magnetism 3D is porous multiple Adsorbent material surface functional groups FTIR result figure is closed, as it can be seen that it is in 3340cm in figure-1There is stronger diffraction maximum at wavelength, this spreads out Penetrate the stretching that peak corresponds to N-H；It is in 1624 cm-1The corresponding diffraction maximum in wavelength place is Fe3O4Particle is formed by after being formed- COO- group；It is in 565 cm-1The corresponding diffraction maximum in wavelength place then shows the presence of Fe-O, also demonstrates Fe3O4Made The presence of standby material surface.
Fig. 2 is the graph of pore diameter distribution of the porous composite adsorbing material of magnetism 3D prepared by the present embodiment, as it can be seen that prepared in figure The aperture of adsorbent material is largely distributed between 4 ~ 10nm.It is 519m that its BET, which calculates specific surface area,3/ g, Kong Rongwei 1.03ml/ g.Prepared adsorbent material pore-size distribution is relatively unified known in figure, has higher specific surface area.
Fig. 3 be the thermal stability analysis of the porous composite adsorbing material of magnetism 3D prepared by the present embodiment as a result, in figure it is found that Material prepared has a preferable thermal stability, and between 20-160 DEG C, material has about 15% mass loss, is mainly inhaled Attached moisture and CO2Desorption, between 160-200, material has about 25% mass loss, the mainly high temperature of surface amine groups It decomposes；Between 200-600 DEG C, adsorbent mass loss is gradually stable.Analysis is the result shows that prepared magnetism 3D is porous compound Adsorbent material normal table can use in 20-160 DEG C of environment.
The above is only the preferred embodiment of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (5)

1. a kind of preparation method of the porous composite adsorbing material of magnetism 3D, it is characterised in that: it includes the following steps:
(1) it disperses graphene oxide in 40~60 ml deionized waters and ultrasonic disperse handles 15~20 min and concentration is made For the graphene oxide solution of 0.3~0.6 mg/ml, then it is slow added into sub- by the four water sulfuric acid that concentration is 5~7 mg/ml The mixed solution that the ferric chloride (FeCl36H2O) that iron and concentration are 10~12 mg/ml is mixedly configured into, solution to be mixed are all added Afterwards, mixed system is ultrasonically treated 20 min, is then stirred for handling, be warming up to mixed system temperature during stir process 40~50 DEG C, when temperature is warming up to preset temperature, sodium hydroxide solution is instilled into mixed system, make its pH value to 10 with On, it is then warming up to 80~90 DEG C again and continues 30~60 min of stir process, is then cooled to room temperature, stands after cooling, The sediment being centrifugated out in mixed system, and after being washed with deionized processing at least 3 times, place it in 90 DEG C true It is dried under Altitude, the product Fe@GO of acquisition；
(2) product Fe@GO obtained is mixed with triethly orthoacetate by the solid-to-liquid ratio of 0.4~0.6ml/mg, then at ultrasound Reason makes product Fe@GO is completely homogeneous to be scattered in triethly orthoacetate, then adds again by p-methyl benzenesulfonic acid and product Fe@GO Mass ratio is that p-methyl benzenesulfonic acid is added in mixed solution by the ratio of 0.02~0.04 mg/mg, and is placed in water in mixed solution In thermal response kettle, 36~48 h of reaction treatment is carried out with 130 DEG C of condition, after the reaction was completed, by sodium hydroxide solution and product Fe@GO addition is than being that the sodium hydroxide solution that concentration is 1 mol/L is added in the ratio of 0.4~0.6 ml/mg, and is vigorously stirred place Manage 4 h, it is after the completion of stirring, mixed system is completely cooling, then be centrifugated out sediment and repeat deionized water washing and from The heart separates at least 2 times, then with acetone washing at least 2 times and is centrifugated out sediment, finally, the sediment isolated is placed in Vacuum drying treatment under room temperature obtains product Fe@GO- ester；
(3) under nitrogen atmosphere, it disperses product Fe@GO- ester in Isosorbide-5-Nitrae-dioxane in the ratio of 5~8 mg/ml, then N,N-Dimethylformamide is instilled in 1 drop/1O ml ratio, 20 min of ultrasonic treatment is then carried out, then presses product Fe@again Oxalyl chloride is added than the ratio for being 3 ml/mg in the addition of GO- ester and oxalyl chloride, and continues to be stirred to react place under nitrogen atmosphere Reason, after complete reaction, the solid content in mixed solution is centrifugated out, and disperse solid content in the ratio of 2 mg/ml It in methylene chloride, is stirred for and is ultrasonically treated 10 min, then again isolate the solid content in solution, and press 2~4 The dispersion concentration ratio of mg/ml is scattered in Isosorbide-5-Nitrae-dioxane, and 20~30 min are then ultrasonically treated, and presses product later Fe GO- ester: polyamine based compound=1: polyamine based compound is added in 10 ratio, then proceedes to 6 h of ultrasonic treatment, then exists It under the conditions of 373 K, is placed in nitrogen atmosphere and is stirred to react, after system reaction to be mixed is completed and cooled down, be centrifugated out solid Then object is scattered in Isosorbide-5-Nitrae-dioxane in the dispersion concentration ratio of 5~10 mg/ml, and be ultrasonically treated 10 min, Ultrasound is completed and after mixed system cooling, is centrifugated out solid content and repeats deionized water washing and centrifuge separation at least 2 times, With acetone washing at least 2 times and solid content is isolated again, disperses deionization in the dispersion concentration ratio of 5~10 mg/ml for it In water, then after 24 h of vacuum drying treatment, solids separation is gone out, obtains the porous composite adsorbing material of magnetic 3D.
2. a kind of preparation method of the porous composite adsorbing material of magnetism 3D according to claim 1, it is characterised in that: step (1) graphene oxide described in is commercial graphene.
3. a kind of preparation method of the porous composite adsorbing material of magnetism 3D according to claim 1, it is characterised in that: step (1) the ferric chloride (FeCl36H2O) mixed configuration that four aqueous ferrous sulfates and concentration that concentration is 5~7 mg/ml in are 10~12 mg/ml At mixed solution and deionized water volume ratio be 100: 40~60.
4. a kind of preparation method of the porous composite adsorbing material of magnetism 3D according to claim 1, it is characterised in that: step (3) the polyamine based compound in is polyethyleneimine or polyamine group ionic liquid.
5. a kind of porous composite adsorbing material of magnetism 3D, it is characterised in that: its preparation side as described in one of Claims 1-4 Method is made.
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