CN104492378B - Magnetic nano composite capable of absorbing perfluorochemicals and preparation method thereof - Google Patents

Magnetic nano composite capable of absorbing perfluorochemicals and preparation method thereof Download PDF

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CN104492378B
CN104492378B CN201410639721.7A CN201410639721A CN104492378B CN 104492378 B CN104492378 B CN 104492378B CN 201410639721 A CN201410639721 A CN 201410639721A CN 104492378 B CN104492378 B CN 104492378B
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nano particle
magnetic
adsorption
ethanol
water
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CN104492378A (en
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梅素容
周雨笋
荆涛
周廷廷
陶芸
周宜开
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Huazhong University of Science and 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials

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Abstract

The invention belongs to the novel material field, and relates to a magnetic nano composite, and especially relates to the magnetic nano composite with high adsorption capacity capable of selectively indentifying perfluorochemicals and a preparation method thereof, which can solve the problem of single identification mechanism and non-ideal selectivity of the adsorbent in prior art. The method is characterized in that the hydrophilic group-modified Fe3O4 nano particles can be taken as a substrate, a one step method is used for synthesizing perfluorooctane and amido-functionalized magnetic nano composite, and the preparation method has the advantages of simple and rapid process, low cost and easy operation. The perfluorochemicals identification by the material is based on fluorine-fluorine interaction and electrostatic attraction, specific recognition capability and adsorption capacity on the target analysis objects can be obviously increased; the prepared magnetic nano composite is in a core-shell structure, surface adsorption endows rapid adsorption power characteristic to the material, the material has good magnetic responsibility, so that the magnetic nano composite has wide application prospect and development space in environment monitoring and pollution controlling fields.

Description

A kind of magnetic nanometer composite material of absorption perfluorochemical and preparation method thereof
Technical field
The invention belongs to field of new, particularly to a kind of high-adsorption-capacity magnetic of Selective recognition perfluorochemical The preparation method of nano composite material.
Background technology
Perfluorochemical belongs to artificial and manufactures chemicals.In its molecular structure, one end is hydrophilic functional group, with carboxyl and Based on sulfonic group, the hydrogen atom in other end alkyl chain is all replaced by fluorine atom.Thus it is unique to impart perfluorochemical Physicochemical properties, such as surface-active, hydro-oleophobicity, heat-resisting acidproof resistance to biodegradable etc., be widely used in weaving, make The fields such as paper, leather, indoor decoration, packaging for foodstuff, fire-fighting and small stores.But, relevant animal experiment shows, entirely Fluorine compounds have bioconcentration, animal used as test body weight can be caused to decline, blood cholesterol level reduces, or even can increase Tumorigenic risk.Additionally, many investigation show, in parent, the perfluorochemical of remaining can be to neonatal weight and the present Growing afterwards causes to significantly affect.At present, perfluorochemical in multiple environmental samples, food and biological sample (as human body Blood and breast milk) in be detected.In May, 2009, PFOS and its esters are classified as new holding by Convention of Stockholm Property organic pollution long, limits it and eliminates in the application of industry and commerce field and progressively by.Even so, in plating, photoelectron And polytetrafluoroethylene (PTFE) manufacturing, PFOS still allow use.Therefore, perfluorochemical has become Environmental Chemistry, public affairs The altogether focus of the area research such as health, how quickly and efficiently to remove or isolating environment sample present in perfluorochemical have Highly important meaning.
Research shows, in the technology of perfluorochemical in existing removal or isolating environment sample, absorption is the easiest, fast Speed, effective measures.The sio of existing multiple adsorbents such as ctab micella parcel at present2, cross-linked chitosan beading, anion hand over Change the perfluorochemical that resin etc. is applied to separate or remove in environmental water sample, these adsorbents are based primarily upon hydrophobic phase interaction With, electrostatic attraction and ion exchange identification perfluorochemical.Due to fe3o4Nano particle has good bio-compatibility, high Specific surface area and quick Magneto separate characteristic, often be used for preparing multifunction magnetic nano material as substrate.For example, Zhao et al. utilizes ctab micella to wrap up fe3o4(xiaoli zhao et al.determinationof perfluorinated compounds in environmental water samples byhigh-performance liquidchromatography-electrospray tandem mass spectrometryusing surfactant- coated fe3o4magnetic nanoparticles as adsorbents.microchemical journal.2011, 98,207-214), amino/octadecyl is modified fe by zhang et al.3o4@sio2Surface (xiaole zhang et al.modifying the surface of fe3o4/sio2magnetic nanoparticles with c18/ nh2mixed group to get an efficientsorbent for anionic organic Pollutants.journal of colloid and interface science.2011,362,107-112), prepare Multifunction magnetic nano-particle, is successfully separated the perfluorochemical in water-outlet body.
In recent years, the research based on fluorochemical in fluorine fluorine interaction Selective Separation complex samples is reported. Yan et al. utilizes the fe of 3- fluorobenzoyl chloride functionalization3o4@sio2Perfluorochemical in@fbc selective extraction environmental water sample (zhihong yan et al.synthesis of 3-fluorobenzoyl chloride functionalized magneticsorbent for highly efficient enrichment of perfluorinated compoundsfrom river water samples.journal of chromatography a.2013,1321,21- 29).In addition, yang et al. is with 1h, 1h, 2h, 2h- perfluoro decyl triethoxysilane is functionalized reagent, synthesizes the perfluor last of the ten Heavenly stems The magnetic mesoporous microballoon f of base functionalization17–fe3o4@msio2, and it is used successfully to the selectivity of perfluorochemical in environment water Separate (lei yang et al.decyl-perfluorinated magneticmesoporousmicrospheres for extraction and analysisperfluorinated compounds in water usingultrahigh- performance liquidchromatography–mass spectrometry.journal of separation science.2012,35,2629-2636).However, the preparation process of above-mentioned functions material is relatively complicated, material is only capable of selecting Property identification perfluoroalkyl chain, but ignore the interaction with hydrophilic functional group, thus the adsorption capacity to perfluorochemical Relatively low.Therefore the present invention plans to build a kind of vertical easy preparation method, synthesizes with specific recognition capability and high power capacity absorption Novel magnetic nano composite material, with realize in environmental sample perfluorochemical rapidly and efficiently separate and removal.
Content of the invention
For above-mentioned adsorbent in problem present on absorption property and technology of preparing, the task of the present invention is to provide one kind High-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical and preparation method thereof, is modified using hydrophilic radical Fe3o4As substrate, " one-step method " synthesis has the magnetic nanometer composite material of core shell structure, and method is simple and efficient, low cost Honest and clean, easily operated.The functional material preparing contains perfluoro capryl and amido bifunctional group, using fluorine fluorine interact and Electrostatic attraction, realizes the specific recognition of perfluorochemical and high power capacity are adsorbed, and to impart material quick for adsorption simultaneously Characteristics of Adsorption-Kinetics.
Realize task of the present invention technical scheme be:
The high-adsorption-capacity magnetic nanometer composite material of the Selective recognition perfluorochemical that the present invention provides is to be coated with Functionalization sio2The magnetic nanoparticle modified through hydrophilic radical of film, described magnetic nanoparticle is fe3o4Nano particle, Described is coated with functionalization sio2The magnetic nanoparticle through hydrophilic radical modification of film is obtained by the following method: by fe3o4Receive Rice grain is added in 0.2～0.4mol/l polyacrylic acid aqueous solution, and the initial concentration of nano particle is 4～12g/l, and 25～40 Continuously stirred ultrasonic 30～60min under the conditions of DEG C, deionized water cyclic washing product removes unconjugated polyacrylic acid, and vacuum is done Dry 12～24h obtains thering is hydrophilic fe3o4Nano particle；By 0.1～0.2mmol (3- aminopropyl) triethoxysilicane Alkane, 0.1～0.2mmol 1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 1～2mmol tetraethyl orthosilicate press material Amount ratio 1:1:8～10 mix as sio2Precursor solution, is added to hydrophily fe3o4Nano particle ethanol/water (2:1～4: 1, v/v) in dispersion, the initial concentration of nano particle is 2～6g/l, adds 1～1.5ml ammoniacal liquor in reaction system simultaneously Solution, continues gentle agitation 6～12h under the conditions of 25～40 DEG C, ethanol/water (1:1, v/v) mixed solution cyclic washing product goes Except unreacted chemicals, it is vacuum dried 12～24h, that is, achieve in the magnetic nanoparticle surface bag modified through hydrophilic radical It is functionalized sio2Film, obtains the high-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical.
The preparation side of the high-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical that the present invention provides Method, comprises the following steps:
Step one: carry out hydrophilic radical modification on magnetic nanoparticle surface；
Step 2: in the magnetic nanoparticle pan coating functional membrane modified through hydrophilic radical.
Magnetic nanoparticle described in step one is fe3o4Nano particle.Described in step one in magnetic nanoparticle table The concrete grammar that face carries out hydrophilic radical modification is；By fe3o4It is water-soluble that nano particle is added to 0.2～0.4mol/l polyacrylic acid In liquid, the initial concentration of nano particle is 4～12g/l, continuously stirred ultrasonic 30～60min, deionization under the conditions of 25～40 DEG C Water cyclic washing product removes unconjugated polyacrylic acid, and vacuum drying 12～24h obtains thering is hydrophilic fe3o4Nanometer Particle.
Described in step 2 in the magnetic nanoparticle pan coating functional membrane modified through hydrophilic radical, be through hydrophilic Magnetic nanoparticle pan coating functionalization sio of base group modification2Film, described in the magnetic Nano modified through hydrophilic radical Grain pan coating functionalization sio2The concrete grammar of film is: by 0.1～0.2mmol (3- aminopropyl) triethoxysilane, 0.1 ～0.2mmol1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 1～2mmol tetraethyl orthosilicate press the ratio of the amount of material 1:1:8～10 mix as sio2Precursor solution, is added to hydrophily fe3o4Nano particle ethanol/water (2:1～4:1, v/v) point In prose style free from parallelism system, the initial concentration of nano particle is 2～6g/l, simultaneously addition 1～1.5ml ammonia spirit in reaction system, 25 Continue gentle agitation 6～12h, ethanol/water (1:1, v/v) mixed solution cyclic washing product removes unreacted under the conditions of～40 DEG C Chemicals, be vacuum dried 12～24h, that is, achieve in the magnetic nanoparticle pan coating functionalization modified through hydrophilic radical sio2Film, obtains the high-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical.
It is an advantage of the current invention that: the fe being modified with hydrophilic radical3o4Nano particle is substrate, and " one-step method " synthesizes to complete Fluorine compounds have the magnetic nanometer composite material of good selectivity and high-adsorption-capacity, and method simplicity is quick, with low cost, easy In operation.Composite identification is interacted and electrostatic attraction based on fluorine fluorine, it is to avoid existing adsorbent recognition mechanism single or Selectively undesirable shortcoming, and the composite of core shell structure has quick surface adsorption kinetic feature, material in addition Expect quick Magneto separate characteristic, wide application prospect will be shown in environmental monitoring and Environmental capacity field and development is empty Between.
Brief description
Fig. 1. the preparation flow of magnetic nanometer composite material and recognition mechanism.
Fig. 2. the fe modifying through hydrophilic radical3o4The transmitted electron of nano-particle (a) and magnetic nanometer composite material (b) shows Micro mirror photo.Appropriate amount of material is disperseed through absolute ethyl alcohol, and carbon coating copper mesh is fished for a small amount of sample, shown by transmitted electron after drying at room temperature Micro mirror (fei tecnai g220 s-twin, U.S.) shoot and obtain.
Fig. 3. the fe modifying through hydrophilic radical3o4Nano-particle (a) and the Fourier transform of magnetic nanometer composite material (b) Infrared spectrum.Sample is mixed with appropriate kbr powder, takes after grinding and be pressed into homogeneous translucent Spherical flasks on a small quantity, thorough Bottom measures it in 400～4000cm by Fourier transformation infrared spectrometer (bruker vertex70, Germany) after being dried-1Scope Interior infrared absorption peak.
Fig. 4. the fe modifying through hydrophilic radical3o4Nano-particle (a) and the hysteresis curve of magnetic nanometer composite material (b)；Sample Product after drying its magnetic characteristic by lakeshore 7400 vibrating specimen magnetometer (equipped with 740h driver and em4-hva Electromagnet, U.S.) measure under room temperature and obtain, magnetic field intensity controls and arrives in the range of+15000oe in -15000oe.
Fig. 5. magnetic nanometer composite material is to the Selective recognition (a) of perfluorochemical and Characteristics of Adsorption-Kinetics (b).
Specific embodiment
With reference to embodiment and material characterization, the preparation method of magnetic nanometer composite material is explained in detail:
Embodiment 1
The preparation of the high-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical
(1) magnetic nanoparticle surface modification hydrophilic radical: concrete preparation process: by fe3o4Nano particle is added to 0.2 In～0.4mol/l polyacrylic acid the aqueous solution, the initial concentration of nano particle is 4～12g/l, persistently stirs under the conditions of 25～40 DEG C Mix ultrasonic 30～60min, deionized water cyclic washing product removes unconjugated polyacrylic acid, be vacuum dried 12～24h Obtain hydrophilic fe3o4Nano particle.
By Fig. 2 (a) as can be seen that each magnetic nano-particle pattern high-visible, particle diameter between 10～20nm, Non-overlapping or few overlapping between grain, therefore hydrophilic radical is modified and be effectively prevent the shortcoming that nano particle is easily reunited.Fig. 3 (a) 1722cm-1Place shows obvious c=o stretching vibration peak, shows carboxyl in fe3o4The presence of nano grain surface, in 592cm-1The absworption peak at place corresponds to the stretching vibration of fe-o.Fig. 4 (a) shows fe3o4Nano particle has good superparamagnetism, satisfies With amount of magnetization for 65emu/g it is easy to externally-applied magnetic field separates.
(2) the surface-functionalized sio of magnetic nanoparticle2Being coated of film: concrete preparation process: by 0.1～0.2mmol (3- Aminopropyl) triethoxysilane, 0.1～0.2mmol 1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 1～2mmol Ratio 1:1:8～10 that tetraethyl orthosilicate presses the amount of material mix as precursor solution, are added to hydrophily fe3o4Nano particle In ethanol/water (2:1～4:1, v/v) dispersion, the initial concentration of nano particle is 2～6g/l, simultaneously in reaction system Add 1～1.5ml ammonia spirit, continue gentle agitation 6～12h under the conditions of 25～40 DEG C, ethanol/water (1:1, v/v) mixes molten Liquid cyclic washing product removes unreacted chemicals, and vacuum drying 12～24h can get Selective recognition perfluorochemical High-adsorption-capacity magnetic nanometer composite material.
Fig. 2 (b) transmission electron microscope shows, each magnetic nanoparticle is all functionalized sio2Film wrap up, film thickness be 4～ 8nm, film absorption ensure that perfluorochemical has quick mass transfer rate in material surface, is easy to realize at short notice ring The removal of target analytes or separation in the sample of border.1083cm in Fig. 3 (b) infrared spectrum-1And 1560cm-1The absworption peak at place divides Not by si-o-si stretching vibration and-nh2Deformation vibration produces, simultaneously in 1145cm-1And 1194cm-1Place can be observed significantly C-f stretching vibration peak, further demonstrates functionalization sio2In fe3o4The formation of nanoparticle surface.Fig. 4 (b) display surface work( Being coated of film can be changed makes fe3o4The magnetic of nano particle decreases, but the saturated magnetization amount of composite still up to 40emu/g, and there is good superparamagnetism, quick separating can be realized in the presence of externally-applied magnetic field.
The Selective recognition evaluation to perfluorochemical for the magnetic nanometer composite material of embodiment 1 preparation, operating procedure is such as Under:
Choose nine kinds of perfluorochemicals, including perfluorohexanesulfonic acid (pfhxs), PFOS (pfos), perfluor heptan Sour (pfhpa), perfluoro caprylic acid (pfoa), perfluoro-pelargonic acid (pfna), perfluoro decanoate (pfda), perfluor undecanoic acid (pfunda), entirely Fluorine lauric acid/dodecanoic acid (pfdoda) and perfluor tetradecylic acid (pfta), six kinds of reference compounds, including perfluorooctanol (6:2ftoh), just pungent Sour (n-oa), 2- fluorophenylacetic acid (2-fpaa), DOPAC (3,4-dhpaa), Florfenicol (ftap) and red mould Plain (ery), is respectively configured the ethanol solution of 0.5mmol/l.20mg magnetic nanometer composite material prepared by embodiment 1 with above-mentioned Each material 10ml ethanol solution mixing, oscillation incubation 18～24h under normal temperature condition, externally-applied magnetic field separation magnetic material, not by In conjunction with compound quantitative (perfluorochemical: lc-ms/ms is detected by corresponding instrument；6:2ftoh and n-oa:gc-ms；2- Fpaa, 3,4-dhpaa, ftap and ery:hplc-uv), the magnetic Nano being calculated per unit mass (g) under this concentration is multiple The adsorbance (mg) to various compounds for the condensation material.Shown in result such as Fig. 5 (a), material shows height to nine kinds of perfluorochemicals Adsorbance, and relatively low to the adsorbance of six kinds of reference compounds it is seen that being interacted based on fluorine fluorine and two kinds of electrostatic attraction work Firmly, this novel magnetic nano composite material can be significantly improved to the Selective recognition of perfluorochemical and adsorption capacity.
The adsorption dynamics adsorption kinetics evaluation to perfluorochemical for the magnetic nanometer composite material, operating procedure is as follows:
Above-mentioned nine kinds of perfluorochemicals are dissolved in ethanol/water (1:9, v/v) mixed solution simultaneously and prepare mixed mark solution, The initial concentration of every kind of compound is 0.5/9mmol/l.20mg magnetic nanometer composite material prepared by embodiment 1 is mixed with 10ml Mark solution mixing, oscillation incubation under normal temperature condition, not combined perfluorinate in solution is measured respectively when 5,10,30,60min The content of compound, draws absorption dynamic curve.By Fig. 5 (b) as can be seen that perfluorochemical can reach absorption within 10min Balance, this is mainly due to film absorption and improves the mass transfer rate in material surface for the compound, such that it is able to realize environment sample The quick removal of perfluorochemical or separation in product.
Embodiment 2
By 0.4g fe3o4Nano particle is added in the 100ml 0.2mol/l polyacrylic acid aqueous solution, holds under the conditions of 30 DEG C The ultrasonic 30min of continuous stirring, products therefrom deionized water cyclic washing removes unconjugated polyacrylic acid, and vacuum drying 12h is The fe with hydrophilic active can be obtained3o4Nano particle.By 0.1mmol (3- aminopropyl) triethoxysilane, 0.1mmol1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 0.8mmol tetraethyl orthosilicate mix as precursor solution, are added to 100ml 2g/l hydrophily fe3o4In nano particle ethanol/water (3:1, v/v) dispersion, add in reaction system simultaneously 1ml ammonia spirit, continues gentle agitation 6h under the conditions of 30 DEG C, ethanol/water (1:1, v/v) mixed solution cyclic washing product removes Unreacted chemicals, the high-adsorption-capacity magnetic Nano that vacuum drying 12h can get Selective recognition perfluorochemical is multiple Condensation material.
Embodiment 3
By 0.8g fe3o4Nano particle is added in the 100ml 0.3mol/l polyacrylic acid aqueous solution, holds under the conditions of 30 DEG C The ultrasonic 45min of continuous stirring, products therefrom deionized water cyclic washing removes unconjugated polyacrylic acid, and vacuum drying 12h is The fe with hydrophilic active can be obtained3o4Nano particle.By 0.15mmol (3- aminopropyl) triethoxysilane, 0.15mmol1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and the mixing of 1.5mmol tetraethyl orthosilicate are molten as precursor Liquid, is added to 100ml 4g/l hydrophily fe3o4In nano particle ethanol/water (3:1, v/v) dispersion, simultaneously to reactant Add 1.25ml ammonia spirit in system, continue gentle agitation 9h under the conditions of 30 DEG C, ethanol/water (1:1, v/v) mixed solution is repeatedly Washed product removes unreacted chemicals, and the high absorption that vacuum drying 12h can get Selective recognition perfluorochemical is held Amount magnetic nanometer composite material.
Embodiment 4
By 1.2g fe3o4Nano particle is added in the 100ml 0.4mol/l polyacrylic acid aqueous solution, holds under the conditions of 30 DEG C The ultrasonic 60min of continuous stirring, products therefrom deionized water cyclic washing removes unconjugated polyacrylic acid, and vacuum drying 12h is The fe with hydrophilic active can be obtained3o4Nano particle.By 0.2mmol (3- aminopropyl) triethoxysilane, 0.2mmol 1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 2mmol tetraethyl orthosilicate mix as precursor solution, are added to 100ml 6g/l hydrophily fe3o4In nano particle ethanol/water (3:1, v/v) dispersion, add in reaction system simultaneously 1.5ml ammonia spirit, continues gentle agitation 12h, ethanol/water (1:1, v/v) mixed solution cyclic washing product under the conditions of 30 DEG C Remove unreacted chemicals, the high-adsorption-capacity magnetic that vacuum drying 12h can get Selective recognition perfluorochemical is received Nano composite material.

Claims (2)

1. a kind of high-adsorption-capacity magnetic nanometer composite material of Selective recognition perfluorochemical, it is to be coated with functionalization sio2The magnetic nanoparticle modified through hydrophilic radical of film, described is coated with functionalization sio2Film through hydrophilic radical modify Magnetic nanoparticle be obtained by the following method: by fe3o4Nano particle is added to 0.2～0.4mol/l polyacrylic acid aqueous solution In, the initial concentration of nano particle is 4～12g/l, continuously stirred ultrasonic 30～60min, deionized water under the conditions of 25～40 DEG C Cyclic washing product removes unconjugated polyacrylic acid, and vacuum drying 12～24h obtains thering is hydrophilic fe3o4Nanometer Grain；By 0.1～0.2mmol (3- aminopropyl) triethoxysilane, 0.1～0.2mmol 1h, 1h, 2h, 2h- perfluoro capryl three Ethoxysilane and 1～2mmol tetraethyl orthosilicate press ratio 1:1:8～10 mixing of the amount of material as precursor solution, add To hydrophily fe3o4In nano particle ethanol/water dispersion, ethanol is 2:1～4:1 with the volume ratio of water, at the beginning of nano particle Beginning concentration is 2～6g/l, adds 1～1.5ml ammonia spirit simultaneously, continue gently to stir under the conditions of 25～40 DEG C in reaction system Mix 6～12h, the ethanol being 1:1 with volume ratio removes unreacted chemicals, vacuum with the mixed solution cyclic washing product of water 12～24h is dried, that is, achieves in magnetic nanoparticle pan coating functionalization sio modified through hydrophilic radical2Film, is selected Selecting property identifies the high-adsorption-capacity magnetic nanometer composite material of perfluorochemical.
2. the preparation side of the high-adsorption-capacity magnetic nanometer composite material of the Selective recognition perfluorochemical described in claim 1 Method it is characterised in that: by fe3o4Nano particle is added in 0.2～0.4mol/l polyacrylic acid aqueous solution, at the beginning of nano particle Beginning concentration is 4～12g/l, continuously stirred ultrasonic 30～60min under the conditions of 25～40 DEG C, and deionized water cyclic washing product removes Unconjugated polyacrylic acid, vacuum drying 12～24h obtains thering is hydrophilic fe3o4Nano particle；By 0.1～0.2mmol (3- aminopropyl) triethoxysilane, 0.1～0.2mmol 1h, 1h, 2h, 2h- perfluoro capryl triethoxysilane and 1～ Ratio 1:1:8～10 that 2mmol tetraethyl orthosilicate presses the amount of material mix as precursor solution, are added to hydrophily fe3o4Nanometer In particle ethanol/water dispersion, ethanol is 2:1～4:1 with the volume ratio of water, and the initial concentration of nano particle is 2～6g/l, Add 1～1.5ml ammonia spirit in reaction system simultaneously, continue gentle agitation 6～12h under the conditions of 25～40 DEG C, use volume Remove unreacted chemicals than the mixed solution cyclic washing product of the ethanol for 1:1 and water, be vacuum dried 12～24h, that is, Achieve in magnetic nanoparticle pan coating functionalization sio modified through hydrophilic radical2Film, obtains Selective recognition perfluorinate The high-adsorption-capacity magnetic nanometer composite material of compound.
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