CN109331783A - Mechanochemistry Magnetic solid phases extracting process, magnetic Nano material and preparation method thereof - Google Patents
Mechanochemistry Magnetic solid phases extracting process, magnetic Nano material and preparation method thereof 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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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
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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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- 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
- B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
Abstract
The invention belongs to analyze processing technology field, and in particular to a kind of mechanochemistry Magnetic solid phases extracting process, comprising: prepare magnetic Nano material；Extraction is vibrated after sample containing analyte, magnetic Nano material and aqueous solution are mixed, so that analyte is adsorbed on magnetic Nano material；Magnetic Nano material is separated from mixed liquor, and carries out supersound washing；And collect eluent and drying.It is organically combined by magnetic Nano material and the extraction of mechanochemistry Magnetic solid phases, improves effect of extracting and production efficiency.
Description
Technical field
The present invention relates to analysis processing technology fields, and in particular to a kind of mechanochemistry Magnetic solid phases extracting process, magnetism
Nano material and preparation method thereof.
Background technique
Nowadays, though with analytical technology progress, in time analyze certain compounds from plant or microorganism still
It is a challenging task.Correctly sampling and sample preparation usually determine the standard of developed method before analysis
True property and applicability.However, due to the complexity of sample matrix, sample pretreatment be it is time-consuming and cumbersome, therefore, exploitation more has
The sample pretreating method of effect is necessary to the bottleneck eliminated in analysis method.Extraction can be improved in effective sample pretreatment
Efficiency is also possible to lead to the superior separation of target analytes and enrichment in some cases, to be further simplified analytic process.
Most of extraction process used at present utilize binary system, the system with the organic solvent of opposed polarity, water and
Their mixture is characterized.These methods include circumfluence distillation, Soxhlet extraction, ultrasound assisted extraction and Microwave-assisted Extraction
It takes.In addition to microwave radiation exaraction, the advantages of said extracted method, is that used extraction conditions are mild, and they the shortcomings that be molten
Agent consumption is high, extraction time is long, extraction efficiency is low.Microwave radiation exaraction is a kind of common extracting method, because of its solvent
Consumption and extraction time are reduced.However, there is the risk being degraded during the extraction process intolerant to thermal compound.In general, traditional mentions
Method is taken to reach target analysis behind cell wall or adipose membrane using solvent combination impulse electric field, heat, microwave and ultrasound radiation
Object, to separate them with cellular component.Alternatively, describing a kind of mechanical force and chemical extraction (MCE) method herein, use
In more effectively being extracted from solid sample matrix under mild physics and electrochemical conditions.MCE is a kind of room temperature process, its benefit
Biomolecule lipid layer and cell are destroyed with sample collision/crushing in liquid with the multi-direction and mechanical force of dedicated ceramic pearl
Wall into the solvent of surrounding, while keeping their chemical integrity to realize the complete release of target compound.With tradition
Extracting method compare, MCE reduces the processing time, while providing higher recovery rate.In order to further increase the effect of MCE
Rate needs for the additional extraction particle (AEP) of smaller size to be added in conventional bead, to realize better sample broke, packet
Include destruction cell wall.Accordingly, it is determined that the AEP material for being suitable for MCE is vital.But it is not immediately clear the size of particle
Influence of the size to this synergistic effect.
After the extraction step, useful separating step is had been considered as with being filtered to remove target compound.It is most of this
Class is using Solid Phase Extraction (SPE), however, there is also some disadvantages by SPE, including long pretreatment time and low extraction effect
Rate.
Therefore, in order to improve effect of extracting and production efficiency, need to design a kind of new mechanochemistry Magnetic solid phases extraction
Method.
Summary of the invention
The object of the present invention is to provide a kind of mechanochemistry Magnetic solid phases extracting process, pass through magnetic Nano material and machinery
Chemical Magnetic solid phases extraction is organically combined, to improve effect of extracting and production efficiency.
In order to solve the above-mentioned technical problems, the present invention provides a kind of mechanochemistry Magnetic solid phases extracting process, comprising: system
Standby magnetic Nano material；Extraction is vibrated after sample containing analyte, magnetic Nano material and aqueous solution are mixed, so that analysis
Object is adsorbed on magnetic Nano material；Magnetic Nano material is separated from mixed liquor, and carries out supersound washing；And collect elution
Liquid and drying.
It optionally, can be by way of external magnet magnetic suck magnetic Nano material, by magnetic Nano material from mixed liquor
Middle separation, while also the analyte being attached on magnetic Nano material can be made to be detached from mixed liquor together.Certainly, this mode can also be with
Method as separation magnetisable material.
Concrete operations are as follows: firstly, magnetic Nano material and aqueous solution are blended in 15.0mL and split by the sample of analyte-containing
It solves in matrix D pipe (its Ceramic Balls for being built-in with several diameter 3.0mm), for mechanochemistry Magnetic solid phases extraction (MCMSPE)；
Secondly, vibration extraction 30-60s, vibration velocity 4.0-5.0m/s on ball mill or biological cracking system, to ensure analyte
It is adsorbed on magnetic Nano material completely；Again, using external magnet magnetic absorption magnetic Nano material so that its from cracking base
It is separated in mixed liquor in matter pipe；Finally, washing magnetic Nano material 1.0- with the organic solvent ultrasound of 1.0-3.0mL
5.0min, eluent is dry, to complete the extraction of analyte.Alternatively, organic by 0.3-1.0mL is re-dissolved in after eluent drying
In solvent, analyzed for UPLC and GC-MS.
Optionally, the magnetic Nano material is with a certain amount of organic solvent washing 3 times, the dry 2-4 under 70 DEG C of vacuum
Hour, to be recycled.
Further, the aqueous solution is the mixed solution of organic solvent and water.
Further, the organic solvent is methanol, ethyl alcohol, acetone, isopropanol, ethyl acetate, n-hexane, one in acetonitrile
Kind is a variety of.
On the other hand, the present invention also provides a kind of preparation methods of magnetic Nano material, comprising: preparation Fe3O4Nanometer
Grain；Modify Fe3O4Nano particle；And the Fe for passing through modificationization3O4Nano particle prepares the magnetic Nano material of core-shell structure.
Further, the preparation Fe3O4The method of nano particle includes: by FeCl3·6H2O and FeCl2·4H2O is dissolving
In deionized water, the stirring and dissolving and at 70~90 DEG C；It is gradually added into concentrated ammonia liquor and stirs；Separate magnetisable material；With distillation
After water and ethyl alcohol circuit sequentially washing, it is dried under vacuum.
Further, the modification Fe3O4The method of nano particle includes: by Fe3O4Thioacetic acid and second is added in nano particle
In the mixed liquor of alcoholic solution and stir evenly；Separate magnetisable material；Respectively for several times with ethyl alcohol and distillation water washing, modificationization is obtained
Fe3O4Nano particle.
Further, the Fe by modificationization3O4Nano particle prepares the method packet of the magnetic Nano material of core-shell structure
It includes: by the Fe of modificationization3O4FeCl is added in nano particle dispersion3·6H2In the mixed liquor of O and ethanol solution；Benzenetricarboxylic acid is added
With the mixed liquor of ethanol solution, and the heating and thermal insulation at 60~80 DEG C；Separate magnetisable material；It is carried out with ethyl alcohol and dimethyl sulfoxide
Washing；And vacuum drying.
Another aspect, the present invention also provides a kind of magnetic Nano materials, comprising: Fe3O4Nano particle and MIL-100
(Fe)；And the MIL-100 (Fe) is suitable for being wrapped in Fe3O4The periphery of nano particle forms core-shell structure.
The invention has the advantages that mechanochemistry Magnetic solid phases extracting process of the invention by magnetic Nano material and
The extraction of mechanochemistry Magnetic solid phases is organically combined, porous structure and biggish specific surface area using magnetic Nano material,
It can selectively be extracted from complicated sample and quickly recycling analyte；In addition, magnetic Nano material can also be in machinery
Facilitate mechanical damage cell wall in chemical Magnetic solid phases extraction, improves extraction yield.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the infrared spectrum of magnetic Nano material；
Fig. 2 is the XRD spectra of magnetic Nano material；
Fig. 3 a is Fe3O4TEM spectrogram；
Fig. 3 b is Fe3O4The TEM spectrogram of@MIL-100 (Fe)；
Fig. 4 is the relational graph for coating the number of plies and surface area, adsorbance；
Fig. 5 a is the SEM image of the tea-leaf power after grinding:
Fig. 5 b is the SEM image of MCE treated tea-leaf power；
Fig. 5 c is the SEM image of MCMSPE treated tea-leaf power.
Specific embodiment
In this embodiment, magnetic Nano material be referred to as magnetic metal organic framework material or
Fe3O4@MIL-100 (Fe) nano particle.Analyte is realized by magnetic Nano material combination mechanochemical treatment
There are many kinds of the modes of the extraction of one step, separation and enrichment, now enumerates one of which, i.e., by magnetic Nano material combination mechanochemistry
Magnetic solid phases extract the organo-chlorine pesticide (analyte) in tealeaves, and are carried out with ultra performance liquid chromatography-gas chromatography-mass spectrography
It tests and analyzes.
In this embodiment, by Fe3O4It combines to form magnetic metal organic framework material with nano material.These core-shell structure copolymers are received
Rice structure is suitable for from complicated sample substrate selectively extracting and quickly recycling analyte.Due to Fe3O4With excellent
Magnetic property and hypotoxicity, therefore its core as adsorbent is selected, this becomes adsorbent from the separation in sample solution
It is convenient controllable.And improved selectivity is shown to certain analytes in extraction process.
The operating procedure of this mechanochemistry Magnetic solid phases extracting process is as follows:
Step S1, prepares magnetic Nano material.
Step S11, Fe3O4The preparation of nano particle: FeCl3·6H2O (2.2g) and FeCl2·4H2O (5.84g) is dissolving
In 100.0mL deionized water, and it is vigorously stirred at a temperature of 80 DEG C to being completely dissolved；Then gradually by concentrated ammonia liquor (10.0mL)
It is added in mixture and stirs 30.0 minutes；The black precipitate isolated with external magnet again, is successively washed with distilled water and ethyl alcohol
It washs three times, finally dry 5.0h obtains Fe under 50.0 DEG C of vacuum3O4Nano particle is with spare.
Step S12, Fe3O4The magnetic Nano material of core-shell structure is formed with MIL-100 (Fe): being taken in step S11
Fe3O4Nano particle (0.1g) and L containing 0.58mmol-1The 20.0mL second of thioacetic acid (mercaptoacetic acid, MAA)
Alcoholic solution is in three-neck flask, mechanical stirring 24.0h；Product is collected with external magnet, respectively for several times with ethyl alcohol and distillation water washing；
By 0.1g thioacetic acid-modification Fe3O4Nano particle is dispersed in 5.0mL FeCl3·6H2O ethanol solution (30.0mmol L-1) in 15.0min；5.0mL (trimesic acid, H containing benzenetricarboxylic acid is added3BTC ethanol solution (30.0mmol L)-1)
In, and kept at 70.0 DEG C
30.0min；It repeats the above process 5 times, it is right with ethyl alcohol and dimethyl sulfoxide (dimethyl sulfoxide, DMSO)
Obtained brown material is washed, so that cleaning solution is limpid supernatant；The dry 6.0h under 70.0 DEG C of vacuum.Repeat 5
The secondary Product Definition successively obtained is Fe3O4@MIL-1, Fe3O4@MIL-2,
Fe3O4@MIL-3, Fe3O4@MIL-4, Fe3O4@MIL-5。
Step S2, the characterization of magnetic metal organic framework material.
FTIR spectrum, x-ray diffraction measurement (XRD) and transmission electron microscopy (TEM) is respectively adopted to survey
Determine the synthetic effect of magnetic metal organic framework material.
Fig. 1 is seen, it can be seen that the synthetic effect of magnetic metal organic framework material is preferable, in 580cm from infrared spectrum-1
Place, due to Fe3O4The presence of Fe-O-Fe key in particle, characteristic absorption band are high-visible.Simultaneously in 1620cm-1And 1385cm-1
It has also been found that two apparent absorption peaks, they are attributed to the asymmetry and midplane extrusion of ionization carboxyl (- COO- anion) at place
Vibration, shows H3The carboxyl of BTC is dissociated into the-COO- anion and FeCl of coordination3·6H2The iron ion of O is mutual by electrostatic
Effect.In addition, in 1113cm-1、779cm-1And 711cm-1Place observed phenyl ring generation=the stretching, extension peak C-O- and δ=C-H it is special
Absorption peak is levied, with Fe3O4And Fe3O4The FT-IR spectrum of@MIL-100 (Fe) is compared, and new absorption band shows magnetic coupling
Organic ligand H in material3The presence of BTC, and show that metal-organic framework is during magnetic core surface gradually assembles
It is successfully formed.
See Fig. 2, x-ray diffraction measurement also demonstrates Fe3O4And Fe3O4The core-shell structure of@MIL-100 (Fe) nano particle.
Fe3O4In 2 θ=30.3 °, 35.4 °, 43.1 °, the typical peaks of 57.4 ° and 62.4 °.In Fe3O4The XRD spectrum of@MIL-100 (Fe)
In remain Fe3O4Most of peak.This shows MOF shell, i.e. MIL-100 (Fe) is in Fe3O4Attachment on nano particle is not
Destroy the crystal structure of metallic framework.
Fe3O42 θ degree diffraction maximums of@MIL-100 (Fe) microballoon at 5 ° and 20 °, this is the particular crystal of MIL-100 (Fe)
Diffraction maximum.Therefore, the Fe of present embodiment synthesis3O4@MIL-100 (Fe) nano particle is by magnetic Fe3O4Core and MOF shell group
At core-shell structure, rather than the physical mixture of two independent components.
See Fig. 3 a and Fig. 3 b；TEM image shows these Fe3O4Nano particle is spherical shape, and diameter is about 15nm.Then, pass through
Gradually the strategy of coating synthesizes MOF shell on magnetic core, forms Fe3O4@MIL-100 (Fe) nucleocapsid NPs.It is observed that nanometer
Grain cluster is by hard Fe3O4Core and MIL-100 (Fe) shell are formed around core, and the size of its cluster is about 60-80nm.
Step S3 extracts pesticide residue.
Pesticide residue analysis has been carried out to four kinds of tealeaves of different regions.All samples are bought from local market
(Taiping Houkui Tea, Mao Feng, Dragon Well tea and Iron Guanyin).By different types of tealeaves and 15.0mL aqueous solution, (organic solvent/water is mixed
Object, ratio 1/9) it is blended in 15.0mL cracking matrix D pipe (being built-in with diameter 3.0mm Ceramic Balls), it is used for MCMSPE；It carries out
The extraction of 40s, to ensure complete absorption of the analyte in solid phase；Then magnetic Nano material is passed through using external magnet and is split
It is separated from mixed liquor the pipe side of solution matrix D pipe；1.0min is eluted with 1.0mL ethyl acetate ultrasound, eluent is dry,
It is re-dissolved in 0.3mL ethyl acetate, is analyzed with UPLC and GC-MS；Above-mentioned experiment carries out 5 times；And magnetic Nano material second
Acetoacetic ester washs 3 times, 6 hours dry under 70 DEG C of vacuum, prepares to reuse.
Step S4 probes into absorption property and the double action of magnetic metal organic framework material.
In order to obtain better extraction efficiency, the several factors for influencing absorption are systematically had studied.Specifically, different packets
The Fe of coating number3O4@MIL-100 (Fe) nano particle shows different absorption behaviors.See Fig. 4, MIL-100-1 in Fig. 4,
MIL-100-2, MIL-100-3, MIL-100-4, MIL-100-5 correspond respectively to Fe3O4@MIL-1、Fe3O4@MIL-2、Fe3O4@
MIL-3、Fe3O4@MIL-4、Fe3O4@MIL-5.Exposed Fe3O4And Fe3O4@MAA is almost without absorption.With MIL-100 (Fe)
The cladding number of plies increase, the adsorbance of organo-chlorine pesticide is by Fe3O4@MIL-1 increases to Fe3O4@MIL-3, then declines, this
It is consistent with the variation of surface area.These results indicate that biggish surface area is conducive to adsorption process.Therefore, Fe is selected3O4@
MIL-3 carries out follow-up study.
See Fig. 5 a, Fig. 5 b and Fig. 5 c, tea leaf powder partial size is successively are as follows: polished tea-leaf power > after the processing of MCE method
Tea-leaf power > by MCMSPE method treated tea-leaf power.These results indicate that when using Ceramic Balls, from ceramics
The energy of ball to sample powder is sufficiently large in an impact, and sample powder rapidly can be ground into lesser fragment.So
And when sample powder is crushed to a certain degree, Ceramic Balls capture is smaller compared with the probability of small sample particle, makes it difficult to it
Be broken into thinner particle.By adding magnetic nanoparticle, lesser addition particle with different acceleration, and with
Original spheres of ceramic collision, plays synergistic effect to sample, to generate thinner sample powder, and improves extraction efficiency.Knot
Fruit shows Fe3O4@MIL-100 (Fe) nano particle enhances mechanochemistry process significantly.
Step S5 probes into the repeatability of magnetic metal organic framework material.
In order to study the reusability of magnetic metal organic framework material, magnetic metal is reused in MCMSPE
Organic framework material.It is washed 3 times with ethyl acetate, it is dry in 70 DEG C of baking ovens, regenerate Fe3O4@MIL-100 (Fe) nanometer
Grain, recycles regenerated Fe3O4@MIL-100 (Fe) nano particle extracts organo-chlorine pesticide from tealeaves.It is reused at five times
Afterwards, the analyte rate of recovery does not have significant changes.Adsorption rate between 83.2-106.2%, these the result shows that: (1) Fe3O4@
MIL-100 (Fe) can be used for the enrichment of organo-chlorine pesticide.(2) using the Fe of layer-by-layer methods synthesis3O4@MIL-100 (Fe) nano particle
It is stable under the conditions employed.During MCMSPE, Fe3O4@MIL-100 (Fe) be it is stable, there is no analytes
It carries.
In conclusion due to magnetic Nano material have more stable structure, large specific surface area, it is easily separated, do not carry point
The features such as analysing object, it both can be used as adsorbent, carry out enrichment and separation to sample, and can assist destroying plant cell wall,
The time of sample pre-treatments stage needs is largely shortened, while decreasing object in the sample pre-treatments stage
Loss.Unique advantage is played in the sample pre-treatments stage, can significantly shorten sample pre-treatments step, to raising target
The qualitative and quantitative analysis of object has great help.Therefore, the mechanochemistry Magnetic solid phases extracting process of the application passes through magnetic
Property nano material and the extraction of mechanochemistry Magnetic solid phases organically combined, it is not only easy to operate, time-consuming is short, dosage is few, cost
It is low, accuracy is high, new thinking can also be provided for the detection of other samples.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of mechanochemistry Magnetic solid phases extracting process characterized by comprising
Prepare magnetic Nano material；
Extraction is vibrated after sample containing analyte, magnetic Nano material and aqueous solution are mixed, so that analyte is adsorbed on magnetic
In property nano material；
Magnetic Nano material is separated from mixed liquor, and carries out supersound washing；And
Collect eluent and drying.
2. extracting process according to claim 1, which is characterized in that
The aqueous solution is the mixed solution of organic solvent and water.
3. extracting process according to claim 1, which is characterized in that
The method of the vibration extraction includes: the vibration extraction 30-60s on ball mill or biological cracking system；
And vibration velocity is 4.0-5.0m/s.
4. extracting process according to claim 1, which is characterized in that
The organic solvent is one of methanol, ethyl alcohol, acetone, isopropanol, ethyl acetate, n-hexane, acetonitrile or a variety of.
5. extracting process according to claim 1, which is characterized in that
The magnetic Nano material is suitable for being recycled after organic solvent washing, vacuum drying.
6. a kind of preparation method of magnetic Nano material characterized by comprising
Prepare Fe3O4Nano particle；
Modify Fe3O4Nano particle；And
Pass through the Fe of modificationization3O4Nano particle prepares the magnetic Nano material of core-shell structure.
7. preparation method according to claim 6, which is characterized in that
The preparation Fe3O4The method of nano particle includes:
By FeCl3·6H2O and FeCl2·4H2O is dissolving in deionized water, and the stirring and dissolving at 70~90 DEG C；
It is gradually added into concentrated ammonia liquor and stirs；
Separate magnetisable material；
Magnetisable material distilled water and ethyl alcohol are circuited sequentially into washing；And
Vacuum drying.
8. preparation method according to claim 6, which is characterized in that
The modification Fe3O4The method of nano particle includes:
By Fe3O4Nano particle is added in the mixed liquor of thioacetic acid and ethanol solution and stirs evenly；
Separate magnetisable material；
Respectively for several times with ethyl alcohol and distillation water washing, the Fe of modificationization is obtained3O4Nano particle.
9. preparation method according to claim 6, which is characterized in that
The Fe by modificationization3O4The method that nano particle prepares the magnetic Nano material of core-shell structure includes:
By the Fe of modificationization3O4FeCl is added in nano particle dispersion3·6H2In the mixed liquor of O and ethanol solution；
The mixed liquor of benzenetricarboxylic acid and ethanol solution, and the heating and thermal insulation at 60~80 DEG C is added；
Separate magnetisable material；
It is washed with ethyl alcohol and dimethyl sulfoxide；And
Vacuum drying.
10. a kind of magnetic Nano material characterized by comprising
Fe3O4Nano particle and MIL-100 (Fe)；And
The MIL-100 (Fe) is suitable for being wrapped in Fe3O4The periphery of nano particle forms core-shell structure.
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