CN106861651A - A kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium - Google Patents
A kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium, superparamagnetism Fe is synthesized using hydro-thermal method3O4Nanocluster, with reference to hexadecane trimethyl ammonium bromide template, using samarium, europium, gadolinium, terbium or dysprosium ion as template ion, using the siloxanes of band functional group as function monomer, there is the molecular engram mesoporous material of high selectivity to samarium, europium, gadolinium, terbium or dysprosium ion using the synthesis of silicate class sol-gal process.The invention has the advantages that the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated have specific recognition ability to samarium, europium, gadolinium, terbium or dysprosium, with magnetic responsiveness high, high-adsorption-capacity, the rate of adsorption high, strong anti acid alkali performance, and can realize simplifying solid-liquor separation flow to the efficiently concentrating of samarium, europium, gadolinium, terbium or dysprosium and while separation.
Description
Technical field
The present invention relates to a kind of preparation of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium
Method, belongs to technical field of material.
Background technology
The high efficiency extraction of low concentration samarium, europium, gadolinium, terbium or dysprosium is separated and typically uses extraction, but existing process to deposit in solution
In high cost, pollution environment, technological process is long, labour intensity is big, poor continuity, be not easy to operate, separating effect and yield
It is undesirable.Metal ingredient should be allowed to separate in process of production thorough, allow it to be easy to reclaim again, and yield the higher the better.This
It is accomplished by improving or changing original correlation technique.Adsorption technology has low, the simple to operate, good selective that consumes energy, can be real
Samarium, europium, gadolinium, terbium or dysprosium efficiently separates in existing low concentration complex system.Therefore, it is necessary to study be suitable for adsorption of Low Concentration
The imprinted material of samarium, europium, gadolinium, terbium or dysprosium.
The content of the invention
It is an object of the invention to provide a kind of magnetic mesoporous trace of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium
The preparation method of material.
To achieve these goals, the present invention by the following method realize by scheme：One kind can separate samarium, europium, gadolinium, terbium or dysprosium
The magnetic mesoporous imprinted material of sandwich structure preparation method, comprise the following steps：
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is（2.2~3.2）：
（6.5~7.8）：（1.5~2.5）, take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then by above-mentioned three and the quality of ethylene glycol
Volume ratio g/mL is calculated as（10.2~13.5）：（5~500）, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol,
Magnetic agitation is allowed to dissolve, and the homogeneous yellow mixed solution that will be obtained is sealed in being transferred to polytetrafluoro hydrothermal reaction kettle, is heated to
6~72h is reacted at 160~250 DEG C, after naturally cool to room temperature, black particle thing is obtained, is washed for several times with ethanol, then carry out
Freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；This step is with ethylene glycol as solvent, polyethylene glycol as stabilizer,
Iron chloride is source of iron, controllable using solvent-thermal method size（1~600nm）, the nanometer Fe that the intensity of magnetization is high and monodispersity is good3O4
Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
Ultrasonically treated 5~the 20min of acid solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and water
The solid-to-liquid ratio g/mL for solving liquid is calculated as（0.05~0.15）:（90~100）, by the nanometer Fe after washing3O4Cluster is distributed to hydrolyzate
In, then 1~100mmol/L containing silicon ion in silicon source to system is slowly added dropwise, and 1~72h is stirred, it is scrubbed, obtain nucleocapsid knot
Structure Fe3O4@nSiO2Carrier；Add generation silicone hydroxyl (Si-OH) and Fe in the hydrolytic process of silicon source3O4The hydroxyl on surface there occurs
Condensation reaction, constantly hydrolytic condensation, finally in nanometer Fe3O4Cluster surface forms the nSiO of densification2Clad；According to waiting to locate
The acidity of solution is managed, the consumption and reaction time for changing silicon source regulate and control nSiO2The thickness of clad, if the acid of pending solution
Spend bigger, required nSiO2The thickness of clad is thicker, then the corresponding amount for adding silicon source is bigger, and the reaction time is more long；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the samarium of band functional group, europium,
The mol ratio of gadolinium, terbium or dysprosium ion is 1：（1.2~1.5）, by the functional polyorganosiloxane monomer of band functional group and target samarium, europium, gadolinium,
Terbium or dysprosium ion solution mix, and obtain function monomer-template molecule host-guest coordination compound；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as（0.05~
0.15）:（0.15~0.25）, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core
Shell structure Fe3O4@nSiO2Support dispersion is in condensation liquid, then the silicon source of 0.3~0.5 mass parts to system is added dropwise in stirring
In, and 1~72h is stirred, it is scrubbed to obtain polymer matrix；In slow hydrolytic condensation, progressively aggregate into containing CTAB certainly
The polymer matrix of assembling micella and samarium, europium, gadolinium, terbium or dysprosium ion dual mould plate；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, using complexing agent or acid solution as the eluant, eluent of target samarium, europium, gadolinium, terbium or dysprosium ion carry out back extraction remove samarium, europium, gadolinium,
Terbium or dysprosium ion, leave the micropore mutually matched with target samarium, europium, gadolinium, terbium or dysprosium ion space structure and action site, i.e.,
Obtain separating the magnetic mesoporous imprinted material IIP-Fe of sandwich structure of samarium, europium, gadolinium, terbium or dysprosium3O4@nSiO2@mSiO2。
The step（1）Polyethylene glycol and ethylene glycol be it is purchased in market analysis it is pure.
The step（2）With（4）Silicon source for tetraethyl orthosilicate, methyl silicate, butyl silicate, positive silicic acid propyl ester or
Other silicate class, are analysis purchased in market pure.
The step（2）Hydrolyzate be made up of the component of following parts by volume：75~85 parts of ethanol, deionized water 15~25
Part, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%.
The step（2）Ethanol for it is purchased in market analysis it is pure.
The step（3）Functional polyorganosiloxane monomer with functional group is F-CH2CH2-NHCH2CH2CH2Si(OMe)3。
The F is-COOH ,-NH2,-POOH or-SH.
The step（3）Target samarium, europium, gadolinium, terbium or dysprosium ion solution be to contain target samarium, europium, gadolinium, terbium or dysprosium ion
The solution of 0.1~2 mol/L, target samarium, europium, gadolinium, terbium or dysprosium ion are carried by its simple substance, oxide, nitric acid thing or chloride etc.
For by soluble solvent（Such as water or inorganic acid）Target samarium, europium, gadolinium, terbium or dysprosium ion solution are obtained after dissolving.
The step（4）Condensation liquid including following parts by volume component：55~65 parts of ethanol, deionized water 75~85
Part, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%, and the CTAB of 0.1~0.4 mass parts is added in liquid mixed above.
The step（5）Complexing agent be β hydroxyls oxime, ethyl acetate, methyl iso-butyl ketone (MIBK) that concentration is 0.1~2mol/L,
The oxide of trioctylphosphine phosphine, tricaprylmethyl ammonium salt, dibutyl carbitol (DBC) or tributyl phosphate.
The step（5）Acid solution be hydrochloric acid solution or sulfuric acid solution that concentration is 0.1~2mol/L.
Gained can separate samarium, europium, gadolinium, terbium or dysprosium the magnetic mesoporous imprinted material of sandwich structure can realize metal target from
Son efficiently separated from liquid to be adsorbed, specifically using imprinted material as adsorbent be added to containing target samarium, europium, gadolinium, terbium or
In the liquid to be adsorbed of dysprosium ion（Target samarium, europium, gadolinium, terbium or dysprosium ion in liquid to be adsorbed are low concentration, 0.1~100mmol/
L）, absorption 10min or so, the concentration of metal ion in the front and rear liquid to be adsorbed of absorption is measured with ICP-OES, adsorption rate is calculated, can
Up to more than 90%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption samarium, europium, gadolinium, terbium or dysprosium as stripping liquid（Stripping liquid and the eluant, eluent one used when synthesizing the adsorbent
Cause）, in different time sampling, with concentration of metal ions, adsorption rate, up to more than 90% in ICP-OES measurement stripping liquids.Desorption
After end, adsorbent is reclaimed using Magneto separate, is dried after being washed to weakly acidic pH, you can recycle.
The present invention is with superparamagnetic core-shell structure Fe3O4@SiO2It is core, with samarium, europium, gadolinium, terbium or dysprosium ion trace and has
Regular meso-hole structure SiO2It is shell, the magnetic mesoporous imprinted material (IIP-Fe of the sandwich structure obtained by preparation3O4@nSiO2@
mSiO2) nanometer samarium, europium, gadolinium, terbium or dysprosium adsorbent can be realized under magnetic force auxiliary and is adsorbed after solution efficiently separate.
The invention has the advantages that：（1）The magnetic mesoporous imprinted material of sandwich structure of gained, not only material structure set
Meter is novel, and the technology of preparing of material functional has innovation, be capable of achieving to the efficiently concentrating of samarium, europium, gadolinium, terbium or dysprosium with separate
While simplify solid-liquor separation flow.（2）Gained can separate the magnetic mesoporous trace material of sandwich structure of samarium, europium, gadolinium, terbium or dysprosium
Material has magnetic responsiveness high, high-adsorption-capacity, the rate of adsorption high, strong anti acid alkali performance, and has special knowledge to samarium, europium, gadolinium, terbium or dysprosium
Other ability.
Specific embodiment
The present invention is further specifically described below by specific embodiment, but is not to be construed as protecting the present invention
Protect the restriction of scope.
Embodiment 1
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 2.2：6.5：1.5,
Take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 10.2 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：5,
By FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, and the homogeneous yellow that will be obtained is mixed
Close during solution is transferred to polytetrafluoro hydrothermal reaction kettle and seal, 72h is reacted at being heated to 160 DEG C, after naturally cool to room temperature, obtain
Black particle thing, is washed 6 times with ethanol, then carries out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 5min of acid solution, then with alternately washing 6 times of ethanol and deionized water, then by nanometer Fe3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL is calculated as 0.05:90, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicic acid second
1mmol/L containing silicon ion in ester to system, and 1h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；The hydrolysis
Liquid is made up of the component of following parts by volume：75 parts of ethanol, 15 parts of deionized water, concentration are 0.5 part of the ammoniacal liquor of 28wt%；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By the functional polyorganosiloxane monomer and gadolinium ion of band functional group
Mol ratio be 1：1.2, by COOH-CH2CH2-NHCH2CH2CH2Si(OMe)3Mix with target gadolinium ion solution, obtain function
Monomer-template molecule host-guest coordination compound；Wherein, target gadolinium ion solution is the solution containing gadolinium ion 0.1mol/L；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.05:
0.15, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@
nSiO2Support dispersion is in condensation liquid, then is added dropwise in the tetraethyl orthosilicate of 0.3 mass parts to system in stirring, and stirs 1h,
It is scrubbed to obtain polymer matrix；The condensation liquid includes the component of following parts by volume：It is 55 parts of ethanol, 75 parts of deionized water, dense
0.5 part of the ammoniacal liquor for 28wt% is spent, and the CTAB of 0.1 mass parts is added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, with Low acid P204Extractant as the eluant, eluent of gadolinium ion carry out back extraction remove gadolinium ion, leave with target samarium, europium,
The micropore that gadolinium, terbium or dysprosium ion space structure and action site are mutually matched, that is, obtain separating the sandwich structure magnetic of gadolinium
The mesoporous imprinted material IIP-Fe of property3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure that gained can separate gadolinium can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target gadolinium ion（It is to be adsorbed
Target gadolinium ion concentration in liquid is 0.1mmol/L）, absorption 10min or so, measure the front and rear liquid to be adsorbed of absorption with ICP-OES
The concentration of middle metal ion, calculates adsorption rate, up to 97%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption gadolinium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 96% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Embodiment 2
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 2.7：7.2：2, take
FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 11.9 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：100,
By FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, and the homogeneous yellow that will be obtained is mixed
Close during solution is transferred to polytetrafluoro hydrothermal reaction kettle and seal, 36h is reacted at being heated to 200 DEG C, after naturally cool to room temperature, obtain
Black particle thing, is washed 5 times with ethanol, then carries out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 10min of acid solution, then with alternately washing 5 times of ethanol and deionized water, then by nanometer Fe3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL be calculated as 0.1:95, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicic acid
10mmol/L containing silicon ion in methyl esters to system, and 36h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；It is described
Hydrolyzate is made up of the component of following parts by volume：80 parts of ethanol, 20 parts of deionized water, concentration are 1 part of the ammoniacal liquor of 28wt%；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the samarium of band functional group, europium,
The mol ratio of gadolinium, terbium or dysprosium ion is 1：1.3, by NH2-CH2CH2-NHCH2CH2CH2Si(OMe)3It is mixed with target europium ion solution
Close, obtain function monomer-template molecule host-guest coordination compound；Wherein, target europium ion solution is to contain europium ion 1mol/L
Solution；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.1:
0.2, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@nSiO2
Support dispersion is in condensation liquid, then is added dropwise in the methyl silicate of 0.4 mass parts to system in stirring, and stirs 36h, through washing
Wash and obtain polymer matrix；The condensation liquid includes the component of following parts by volume：60 parts of ethanol, 80 parts of deionized water, concentration are
1 part of the ammoniacal liquor of 28wt%, and the CTAB of 0.3 mass parts is added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
Mesoporous, the sulfuric acid solution using concentration as 1mol/L carries out back extraction and removes europium ion as the eluant, eluent of europium ion, leaves and target
The micropore that europium ion space structure and action site are mutually matched, that is, obtain the magnetic mesoporous print of sandwich structure of energy Separation Europium
Mark material IIP-Fe3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure of gained energy Separation Europium can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target europium ion（It is to be adsorbed
Target europium ion concentration in liquid is 10mmol/L）, absorption 10min or so, with the ICP-OES front and rear liquid to be adsorbed of measurement absorption
The concentration of metal ion, calculates adsorption rate, up to 98%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption europium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 98% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Embodiment 3
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is 3.2： 7.8：2.5,
Take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then it is calculated as 13.5 by the mass volume ratio g/mL of above-mentioned three and ethylene glycol：
500, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol, and magnetic agitation is allowed to dissolve, the homogeneous Huang that will be obtained
Mixture of colours solution is sealed in being transferred to polytetrafluoro hydrothermal reaction kettle, and 1h is reacted at being heated to 250 DEG C, after naturally cool to room temperature,
Black particle thing is obtained, is washed for several times with ethanol, then carry out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster salt of 0.1mol/L
The ultrasonically treated 20min of acid solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and hydrolyzate
Solid-to-liquid ratio g/mL be calculated as 0.15:100, by the nanometer Fe after washing3O4Cluster is distributed in hydrolyzate, then is slowly added dropwise positive silicon
100mmol/L containing silicon ion in acid butyl ester to system, and 72h is stirred, it is scrubbed, obtain core shell structure Fe3O4@nSiO2Carrier；
The hydrolyzate is made up of the component of following parts by volume：85 parts of ethanol, 25 parts of deionized water, concentration are the ammoniacal liquor 1.5 of 28wt%
Part；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the samarium of band functional group, europium,
The mol ratio of gadolinium, terbium or dysprosium ion is 1：1.5, by POOH-CH2CH2-NHCH2CH2CH2Si(OMe)3With target dysprosium ion solution
Mixing, obtains function monomer-template molecule host-guest coordination compound；Wherein, target dysprosium ion solution is to contain dysprosium ion 2mol/L
Solution；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as 0.15:
0.25, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core shell structure Fe3O4@
nSiO2Support dispersion is in condensation liquid, then is added dropwise in the butyl silicate of 0.5 mass parts to system in stirring, and stirs
72h, it is scrubbed to obtain polymer matrix；The condensation liquid includes the component of following parts by volume：65 parts of ethanol, deionized water 85
Part, concentration are 1.5 parts of the ammoniacal liquor of 28wt%, and the CTAB of 0.4 mass parts are added in liquid mixed above；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, leaves orderly on polymer matrix
It is mesoporous, with Low acid P204Extractant as the eluant, eluent of target dysprosium ion carry out back extraction remove dysprosium ion, leave with target dysprosium from
The subspace micropore that structurally and functionally site mutually matches, that is, obtain the magnetic mesoporous trace material of sandwich structure of energy separation of Dy
Material IIP-Fe3O4@nSiO2@mSiO2。
The magnetic mesoporous imprinted material of sandwich structure of gained energy separation of Dy can realize target metal ions from liquid to be adsorbed
In efficiently separate, be specifically added to imprinted material as adsorbent in the liquid to be adsorbed containing target dysprosium ion（It is to be adsorbed
Dysprosium ion concentration in liquid is 100mmol/L）, absorption 10min or so, measure golden in liquid to be adsorbed before and after adsorbing with ICP-OES
Belong to the concentration of ion, calculate adsorption rate, up to 96%.
The adsorbent for terminating is adsorbed to be reclaimed using Magneto separate, and the washing that adds water is subsequently adding complexing agent or acid to weakly acidic pH
Solution carries out desorption dysprosium as stripping liquid（Stripping liquid is consistent with the eluant, eluent used when synthesizing the adsorbent）, taken in different time
Sample, with concentration of metal ions, adsorption rate, up to 97% in ICP-OES measurement stripping liquids.After desorption terminates, adsorbent uses Magneto separate
Reclaim, dried after being washed to weakly acidic pH, you can recycle.
Claims (9)
1. a kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium, its feature
It is to comprise the following steps：
（1）Nanometer Fe3O4The preparation of cluster：By FeCl3 .6H2O：Sodium acetate：The mass ratio of polyethylene glycol is（2.2~3.2）：
（6.5~7.8）：（1.5~2.5）, take FeCl3 .6H2O, sodium acetate and polyethylene glycol, then by above-mentioned three and the quality of ethylene glycol
Volume ratio g/mL is calculated as（10.2~13.5）：（5~500）, by FeCl3 .6H2O, sodium acetate and polyethylene glycol are added in ethylene glycol,
Magnetic agitation is allowed to dissolve, the mixed solution sealing that will be obtained, and 6~72h is reacted at being heated to 160~250 DEG C, treats natural cooling
To room temperature, black particle thing is obtained, washed for several times with ethanol, then carry out freeze-drying or vacuum drying, that is, obtain nanometer Fe3O4
Cluster；
（2）Core shell structure Fe3O4@nSiO2The preparation of carrier：By step（1）Gained nanometer Fe3O4The cluster hydrochloric acid of 0.1mol/L
Ultrasonically treated 5~the 20min of solution, then alternately washed for several times, then by nanometer Fe with ethanol and deionized water3O4Cluster and hydrolysis
The solid-to-liquid ratio g/mL of liquid is calculated as（0.05~0.15）:（90~100）, by the nanometer Fe after washing3O4Cluster is distributed to hydrolyzate
In, then 1~100mmol/L containing silicon ion in silicon source to system is slowly added dropwise, and 1~72h is stirred, it is scrubbed, obtain nucleocapsid knot
Structure Fe3O4@nSiO2Carrier；
（3）The preparation of function monomer-template molecule host-guest coordination compound：By functional polyorganosiloxane monomer and the samarium of band functional group, europium,
The mol ratio of gadolinium, terbium or dysprosium ion is 1：（1.2~1.5）, by the functional polyorganosiloxane monomer of band functional group and target samarium, europium, gadolinium,
Terbium or dysprosium ion solution mix, and obtain function monomer-template molecule host-guest coordination compound；
（4）The preparation of polymer matrix：By core shell structure Fe3O4@nSiO2The ratio g/mmol of carrier and complex is calculated as（0.05~
0.15）:（0.15~0.25）, by step（3）Gained function monomer-template molecule host-guest coordination compound and step（2）Gained core
Shell structure Fe3O4@nSiO2Support dispersion is in condensation liquid, then the silicon source of 0.3~0.5 mass parts to system is added dropwise in stirring
In, and 1~72h is stirred, it is scrubbed to obtain polymer matrix；
（5）By acetone extraction method removing step（4）CTAB in resulting polymers parent, using complexing agent or acid solution as washing
De- agent carries out back extraction and removes samarium, europium, gadolinium, terbium or dysprosium ion, that is, obtain separating the sandwich structure magnetic of samarium, europium, gadolinium, terbium or dysprosium
The mesoporous imprinted material of property；
The acid solution is the hydrochloric acid solution or sulfuric acid solution that concentration is 0.1~2mol/L.
2. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：It is pure that the polyethylene glycol, ethylene glycol and ethanol are analysis purchased in market.
3. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（2）With（4）Silicon source for tetraethyl orthosilicate, methyl silicate, butyl silicate,
Positive silicic acid propyl ester or other silicate class, are analysis purchased in market pure.
4. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（2）Hydrolyzate be made up of the component of following parts by volume：75~85 parts of ethanol, go
15~25 parts of ionized water, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%.
5. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（3）Functional polyorganosiloxane monomer with functional group is F-CH2CH2-NHCH2CH2CH2Si
(OMe)3。
6. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 5
Preparation method, it is characterised in that：The F is-COOH ,-NH2,-POOH or-SH.
7. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（3）Target samarium, europium, gadolinium, terbium or dysprosium ion solution be containing target samarium, europium,
The solution of gadolinium, terbium or the mol/L of dysprosium ion 0.1~2.
8. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（4）Condensation liquid including following parts by volume component：55~65 parts of ethanol, go from
75~85 parts of sub- water, concentration are 0.5~1.5 part of the ammoniacal liquor of 28wt%, and 0.1~0.4 mass parts are added in liquid mixed above
CTAB。
9. the magnetic mesoporous imprinted material of the sandwich structure that samarium, europium, gadolinium, terbium or dysprosium can be separated according to claim 1
Preparation method, it is characterised in that：The step（5）Complexing agent be P204Extractant.
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Application publication date: 20170620 |