CN104258826B - A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application - Google Patents
A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application Download PDFInfo
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- CN104258826B CN104258826B CN201410467787.2A CN201410467787A CN104258826B CN 104258826 B CN104258826 B CN 104258826B CN 201410467787 A CN201410467787 A CN 201410467787A CN 104258826 B CN104258826 B CN 104258826B
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
Abstract
The invention provides a kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application, belong to material preparation technology and separation technology field；First prepare amino functional mesoporous material, then prepare the mesoporous material of grafted chain transfer agent, obtain mesoporous material surface ion imprinted polymer with template ion, function monomer, crosslinking agent, initiator for reaction；Solve that surface polymer layer thickness is uncontrollable, template molecule because of embedded deep and cannot elute, the problem such as the rate of adsorption is slow；Being mainly used under respective metal ion in adsorption aqueous solution, room temperature having good adsorption effect, adsorption capacity is big and effectively reduces non-specific adsorption.
Description
Technical field
The invention belongs to environment functional material technical applications, especially a kind of activity/controlled mesoporous material surface from
Sub-imprinted polymer and preparation method and application.
Background technology
Along with the development of China's nuclear industry, the discharge capacity of middle low-activity waste water is continuously increased.Wherein, middle low-activity
Metallic element is then the important component part of middle low-activity waste water.Owing to the harm of middle radioactive metal ion has stronger
Disguise, is difficult to be noticeable and its harmfulness not easily passs through the method for chemistry, physics or biology and eliminates, and therefore realizes it and effectively locates
Reason is particularly important.Traditional processing method (such as evaporation concentration method, chemical precipitation method and ion-exchange) is usually present effect
Rate is low, complex operation and selectivity difference etc. problem.Therefore, set up low-activity metal pollutant in effective exclusive type to process
Modeling sense is great.
Molecular imprinting is a kind of poly-for preparing the trace to a certain specific template molecule with singleness identity
The technology of compound (MIPs).Object to be separated and crosslinking agent carry out in polymer monomer solution copolymerization prepare
Granule medium, then elutes away the object being embedded in medium, just obtains the molecule to object with singleness identity
Imprinted polymer.When object is metal ion, then can be referred to as ion imprinted polymer (IIPs).Surface ion trace skill
Art, is the immunoblot method imprinted layer with recognition site being combined in stromal surface.It can be efficiently against tradition trace skill
In art imprinted cavity embedded deeply, template ion wash-out difficulty and the shortcoming such as mass transfer velocity is slow, thus reach to improve trace and gather
The purpose of compound adsorption efficiency.Mesoporous material SBA-15 is because of its homogeneous aperture, big specific surface area, bigger pore volume and very
Good surface is modified characteristic and is widely used as the host material of surface imprinted process.
In surface imprinted polymerization field, in order to overcome the defect of conventional free radical polymerization existence (as polymer architecture can not
Control, template binding site heterogeneity), Controlled/Living Radical Polymerization (CRP) is gradually introduced the system of surface imprinted polymer
Standby process.Wherein, reversible addion-fragmentation chain transfer (RAFT) is polymerized, and is polymerized as the typical CRP of one, in recent years by gradually
Introduce the preparation process of molecular imprinted polymer on surface.But, as far as we know, report related to this nearly all concentrates on
In the preparation of MIP, and the concern to IIP is few.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of with mesoporous SBA-15 as host material, employing can
Inverse addition-fracture chain tra nsfer (RAFT) polymerization preparation has the metal ion imprinted polymer of controlled architecture..
The present invention realizes above-mentioned technical purpose by techniques below means.
The preparation method of a kind of activity/controlled mesoporous material surface ion imprinted polymer, comprises the steps:
I, mesoporous material SBA-15 it is purified and activates；
II, the preparation of amino functional mesoporous material: by above-mentioned SBA-15 and silane coupler in toluene in anaerobic bar
Refluxing under part, product is scrubbed, dry；
III, the preparation of the mesoporous material of grafted chain transfer agent: above-mentioned amino functional mesoporous material is added to chain-transferring agent
Acetonitrile solution 1 in, ultrasonic rear ice bath stand, add N, N-dicyclohexylcarbodiimide acetonitrile solution 2, the most instead
Should, product is scrubbed, dry；
IV, the preparation of ion imprinted polymer: by template ion, function monomer, crosslinking agent, above-mentioned grafted chain transfer agent
Mesoporous material stirs in methyl alcohol and acetonitrile mixture, adds initiator, in water-bath under oxygen free condition, molten with EDTA
Liquid washs and detects to metal ion washes clean, dries product.
In such scheme, described SBA-15 purifies and with activation method is: SBA-15 is stood at 80 DEG C aging 12 ~
48 h, are washed with deionized, the SBA-15 that 18 ~ 72 h that reflux in ethanol must purify；Being placed on concentration is 1.0 ~ 3.0
Reflux in mol/L hydrochloric acid solution 24 h, is dried after being washed till neutrality.
In such scheme, silane coupler described in step II is 3-aminopropyl triethoxysilane or 3-aminopropyl front three
TMOS；
Described toluene consumption is that every 6.25 ~ 18.75 g SBA-15 are scattered in 1 L toluene, described silane coupled agent concentration
It is 0.05 ~ 0.15 mol/L；
Described return time is 10 ~ 20 h.
In such scheme, in such scheme, chain-transferring agent described in step III is 2-(dodecyl trithiocarbonate
Base)-2 Methylpropionic acid (TTCA)；
Described acetonitrile content is that every 5.0 ~ 10.0 g amino functional mesoporous materials are placed in 1 L acetonitrile solution, described chain
The concentration of transfer agent is 0.01 ~ 0.03 mol/L, described N, N-dicyclohexylcarbodiimide concentration in acetonitrile 2 is 0.04 ~
0.08 mol/L；
The described reaction time is 10 ~ 20 h.
In such scheme, template ion described in step IV is for being provided by soluble metallic salt, and described function monomer is first
Base acrylic acid, described crosslinking agent is ethylene glycol dimethacrylate or N, N '-methylene-bisacrylamide, and described initiator is
Azodiisobutyronitrile；
In described mixed liquor, methyl alcohol is 4:1 with the volume ratio of acetonitrile, and described template ion concentration is 5.0 ~ 15.0 mmol/
L, the concentration of described function monomer and crosslinking agent is respectively 20.0 ~ 60.0 mmol/L and 50.0 ~ 150.0 mmol/L, described in draw
Send out the mesoporous material that agent consumption is every 50 ~ 100 mg grafted chain transfer agents and add 4 ~ 8 mg initiators, described EDTA solution dense
Degree is 0.1 mol/L；
Described bath temperature is 55 ~ 65 DEG C, and the water-bath time is 6 ~ 24 h.
In such scheme, described template ion at least includes nickel, iron, caesium, copper, strontium, mercury, cobalt, cadmium, manganese, zinc.
In such scheme, described method prepares activity/controlled mesoporous material surface ion imprinted polymer.
Further, described activity/controlled mesoporous material surface ion imprinted polymer is corresponding in adsorption aqueous solution
Ion.
Prepared metal ion trace adsorbent is carried out Dynamic Adsorption and static selective absorption experiment, as follows
Carry out:
Dynamic Adsorption is tested: ion imprinted polymer loads Dynamic Adsorption post, is passed through deionized water 10 min, by metal
Solion (pH is consistent with deionized water) is passed through adsorption column, and controls loading flow velocity with peristaltic pump, circulates water control by the external world
The temperature of metal ion solution processed, finally connects efflux with 10 mL color-comparison tubes respectively in different time sections, uses Atomic absorption
Spectroscopic methodology surveys concentration of metal ions.
Static selective absorption experiment: preparation many kinds of metal ions and the mixed liquor of object ion, the concentration of every kind of ion
Unanimously, take the solution of the 25 above-mentioned preparations of mL in colorimetric cylinder, add ion imprinted polymer, test fluid is placed in 25 DEG C of water-baths
Middle standing 12 h, is centrifugally separating to obtain supernatant, with atomic absorption spectrum and plasma emission spectrometer measure each metal from
Sub-concentration.
Present invention have the advantage that
(1) make host material with SBA-15, prepare metal ion imprinted polymer at host surface, it is to avoid tradition
The problems such as the template ion wash-out difficulty that trace polymerization exists, and the trace adsorbent obtained has, and specific surface area is big, machinery is strong
The advantages such as degree is high, recognition site is survivable, are greatly improved the adsorption capacity of imprinted polymer and effectively reduce non-specific
Property absorption；
(2) the successful grafting on SBA-15 surface of the RAFT reagent is achieved by simple rear Graft Method, thus by RAFT
Free radical activity controllable polymerization be incorporated into surface imprinted during, synthesize the cesium ion imprinted polymer with controllable appearance；
(3) the metal ion imprinted polymer utilizing the present invention to obtain has higher adsorption capacity, has quickly suction
Attached kinetic property and the specific recognition ability to special metal ion.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 and amplifies transmission electron microscope picture, Fig. 1 (a) and Fig. 1 (c) be respectively SBA-15 and
The scanning electron microscope (SEM) photograph of Cs (I) ion blotting adsorbent；Fig. 1 (b) and Fig. 1 (d) is that SBA-15 and Cs (I) ion blotting is inhaled respectively
The amplification transmission electron microscope picture on attached dose of surface.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is also
It is not limited to this.
Embodiment 1:
(1) mesoporous material SBA-15 it is purified and activates: weighing 2 mg SBA-15 and stand aging under 80 ° of C
12 h, then fully wash by deionized water, the SBA-that the 18 h removing residual templates that reflux the most in ethanol obtain purifying
15；SBA-15 after purification is placed in 1.0 mol/L hydrochloric acid solutions 24 h that reflux, is dried after being washed till neutrality and i.e. realizes SBA-
The activation of 15 surface Si-OH；
(2) preparation of amino functional mesoporous material: the SBA-15 taking 0.25 g step (1) gained is scattered in 40 mL first
In benzene, being slowly dropped into 0.47 mL 3-aminopropyl triethoxysilane, logical nitrogen seals and is stirred at reflux 10 h, and products therefrom is successively
With toluene, ethanol washing, under 60 ° of C, after vacuum drying, i.e. obtain amino functional mesoporous material；
(3) preparation of the mesoporous material of grafted chain transfer agent: by 0.073 g 2-(dodecyl trithiocarbonic acid ester group)-
2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, adds the mesoporous material of amino functional of 0.10 g step (2) gained
Material, stands after ultrasonic 10 min in ice bath；Adding 82.5 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, under room temperature
Stir 10 h；Products therefrom acetonitrile washs, and ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent；
(4) preparation of cesium ion trace adsorbent: take 8.4 mg cesium chlorides (CsCl) and be dissolved in 10 mL methyl alcohol and acetonitrile and mix
Close in liquid (methyl alcohol/acetonitrile=4/1, V/V), add 17 μ L methacrylic acids and 95 μ L GDMAs, then add
Entering the mesoporous material of the grafted chain transfer agent of 50 mg step (3) gained, be stirring evenly and then adding into 4 mg bis-isobutyronitriles, nitrogen is protected
Protect, 60 ° of C water-bath 8 h；Wash the 12 above-mentioned products of h to remove metal ion with 0.1 mol/L EDTA solution, repeat to wash
Wash 5 times, and by the concentration of cesium ion in aas determination eluent, it is ensured that metal ion is removed clean, by gained
Cesium ion trace adsorbent dry under 60 ° of C.
From Fig. 1 (a) and Fig. 1 (c), the cesium ion surface imprinted polymer of preparation maintains the rule of mesoporous SBA-15
Corynebacterium structure；The partial enlargement transmission electron microscope picture (Fig. 1 (b) and Fig. 1 (d)) on the two surface the most preferably illustrates RAFT trace
Polymer foil is grafted to the surface of mesoporous SBA-15 effectively and prepared Cs (I) ion blotting adsorbent maintains well
The excellent pore passage structure of matrix SBA-15.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, is passed through the deionization that pH is 6
10 mg/L cesium ion solution (pH=6), after deionized water flows completely out, are passed through adsorption column, and use peristaltic pump by water 10 min
Control loading flow velocity and be respectively 1.0,3.0,5.0 mL/min, control the temperature of metal ion solution respectively by extraneous recirculated water
Be 25,35,55 ° of C, connect efflux continuously with 10 mL color-comparison tubes, sample interval is 5,8,12,15,30,45,
60,75,90,120,150,180,360,720 min, and measure with atomic absorption spectrophotometer (FAAS) that to meet sample Cs (I) dense
Degree.
Result shows, 25 ° of C, flow velocity 1.0 mL min-1Time to record the equilibrium adsorption capacity of connect sample Cs (I) be 6.18
Mg/g, and balance is reached when T=70 min.Through comparing discovery, temperature is the lowest, and flow velocity is the least, and adsorption capacity is the biggest, and inhales
Attached balance required time is the longest.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and mesh
Mark ion Cs () mixed liquor, the concentration of every kind of ion is 10 mg/L, takes the solution of the 25 above-mentioned preparations of mL in colorimetric cylinder
In, regulating pH value with watery hydrochloric acid or weak aqua ammonia is 6.0, add 20 mg Cs () ion imprinted polymer, test fluid is placed in 25
° C water-bath stands 12 h, is centrifugally separating to obtain supernatant, measure not with plasma emission spectrometer with atomic absorption spectrum
Adsorbed each concentration of metal ions.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), and wherein Cs (I) is relative to competitive Adsorption
Ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), the selectivity factor of Cd (II) are respectively 5.24, and 5.12,
5.78,3.38,7.32, and 6.89, rather than trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding choosing
Select property coefficient and be respectively 1.38,0.69,1.05,2.14,1.31,0.85.
Embodiment 2:
(1) mesoporous material SBA-15 it is purified and activates: weighing 2 mg SBA-15 and stand aging under 80 ° of C
24 h, then fully wash by deionized water, the SBA-that the 50 h removing residual templates that reflux the most in ethanol obtain purifying
15；SBA-15 after purification is placed in 2.0 mol/L hydrochloric acid solutions 24 h that reflux, is dried after being washed till neutrality and i.e. realizes SBA-
The activation of 15 surface Si-OH；
(2) preparation of amino functional mesoporous material: the SBA-15 taking 0.5 g step (1) gained is scattered in 40 mL toluene
In, it being slowly dropped into 0.94 mL 3-aminopropyl triethoxysilane, logical nitrogen seals and is stirred at reflux 15 h, and products therefrom is used successively
Toluene, ethanol wash, and i.e. obtain amino functional mesoporous material under 60 ° of C after vacuum drying；
(3) preparation of the mesoporous material of grafted chain transfer agent: by 0.146 g 2-(dodecyl trithiocarbonic acid ester group)-
2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, adds the mesoporous material of amino functional of 0.15 g step (2) gained
Material, stands after ultrasonic 10 min in ice bath；Add 123.8 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, room temperature
Lower stirring 15 h；Products therefrom acetonitrile washs, and ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent；
(4) preparation of cesium ion trace adsorbent: take 16.8 mg cesium chlorides (CsCl) and be dissolved in 10 mL methyl alcohol and acetonitrile and mix
Close in liquid (methyl alcohol/acetonitrile=4/1, V/V), add 34 μ L methacrylic acids and 190 μ L GDMAs, then
Add the mesoporous material of the grafted chain transfer agent of 75 mg step (3) gained, be stirring evenly and then adding into 6 mg bis-isobutyronitriles, nitrogen
Protection, 60 ° of C water-bath 8 h；Wash the 12 above-mentioned products of h to remove metal ion with 0.1 mol/L EDTA solution, repeat
Wash 5 times, and by the concentration of cesium ion in aas determination eluent, it is ensured that metal ion is removed clean, by institute
The cesium ion trace adsorbent obtained is dried under 60 ° of C.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, is passed through the deionization that pH is 6
10 mg/L cesium ion solution (pH=6), after deionized water flows completely out, are passed through adsorption column, and use peristaltic pump by water 10 min
Control loading flow velocity and be respectively 1.0,3.0,5.0 mL/min, control the temperature of metal ion solution respectively by extraneous recirculated water
Be 25,35,55 ° of C, connect efflux continuously with 10 mL color-comparison tubes, sample interval is 5,8,12,15,30,45,
60,75,90,120,150,180,360,720 min, and measure with atomic absorption spectrophotometer (FAAS) that to meet sample Cs (I) dense
Degree.
Result shows, 25 ° of C, flow velocity 1.0 mL min-1Time to record the equilibrium adsorption capacity of connect sample Cs (I) be 6.33
Mg/g, and balance is reached when T=90 min.Through comparing discovery, temperature is the lowest, and flow velocity is the least, and adsorption capacity is the biggest, and inhales
Attached balance required time is the longest.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and mesh
Mark ion Cs () mixed liquor, the concentration of every kind of ion is 10 mg/L, takes the solution of the 25 above-mentioned preparations of mL in colorimetric cylinder
In, regulating pH value with watery hydrochloric acid or weak aqua ammonia is 6.0, add 20 mg Cs () ion imprinted polymer, test fluid is placed in 25
° C water-bath stands 12 h, is centrifugally separating to obtain supernatant, measure not with plasma emission spectrometer with atomic absorption spectrum
Adsorbed each concentration of metal ions.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), and wherein Cs (I) is relative to competitive Adsorption
Ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), the selectivity factor of Cd (II) are respectively 7.67, and 8.72,
9.31,5.73,11.25 and 8.54, rather than trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding choosing
Select property coefficient and be respectively 0.97,1.26,1.24,0.77,0.95,1.15.
Embodiment 3:
(1) mesoporous material SBA-15 it is purified and activates: weighing 2 mg SBA-15 under 80 ° of C, stand aging 48
H, then fully washs by deionized water, the SBA-15 that the 72 h removing residual templates that reflux the most in ethanol obtain purifying；
SBA-15 after purification is placed in 3.0 mol/L hydrochloric acid solutions 24 h that reflux, is dried after being washed till neutrality and i.e. realizes SBA-15 table
The activation of face Si-OH；
(2) preparation of amino functional mesoporous material: the SBA-15 taking 0.75 g step (1) gained is scattered in 40 mL first
In benzene, being slowly dropped into 1.41 mL 3-aminopropyl triethoxysilanes, logical nitrogen seals and is stirred at reflux 20 h, and products therefrom is successively
With toluene, ethanol washing, under 60 ° of C, after vacuum drying, i.e. obtain amino functional mesoporous material；
(3) preparation of the mesoporous material of grafted chain transfer agent: by 0.219 g 2-(dodecyl trithiocarbonic acid ester group)-
2 Methylpropionic acid (TTCA) is dissolved in 20 mL acetonitrile solutions, adds the amino functional mesoporous material of 0.2 g step (2) gained,
Stand in ice bath after ultrasonic 10 min；Add 165.0 mg N, the acetonitrile solution of N-dicyclohexylcarbodiimide, stir under room temperature
Mix 20 h；Products therefrom acetonitrile washs, and ambient temperature in vacuum is drying to obtain the mesoporous material of grafted chain transfer agent；
(4) preparation of cesium ion trace adsorbent: take 25.2 mg cesium chlorides (CsCl) and be dissolved in 10 mL methyl alcohol and acetonitrile and mix
Close in liquid (methyl alcohol/acetonitrile=4/1, V/V), add 51 μ L methacrylic acids and 285 μ L GDMAs, then
Add the mesoporous material of the grafted chain transfer agent of 100 mg step (3) gained, be stirring evenly and then adding into 8 mg bis-isobutyronitriles, nitrogen
Protection, 60 ° of C water-bath 8 h；Wash the 12 above-mentioned products of h to remove metal ion with 0.1 mol/L EDTA solution, repeat
Wash 5 times, and by the concentration of cesium ion in aas determination eluent, it is ensured that metal ion is removed clean, by institute
The cesium ion trace adsorbent obtained is dried under 60 ° of C.
Dynamic Adsorption is tested: 0.1 g cesium ion trace adsorbent is loaded Dynamic Adsorption post, is passed through the deionization that pH is 6
10 mg/L cesium ion solution (pH=6), after deionized water flows completely out, are passed through adsorption column, and use peristaltic pump by water 10 min
Control loading flow velocity and be respectively 1.0,3.0,5.0 mL/min, control the temperature of metal ion solution respectively by extraneous recirculated water
Be 25,35,55 ° of C, connect efflux continuously with 10 mL color-comparison tubes, sample interval is 5,8,12,15,30,45,
60,75,90,120,150,180,360,720 min, and measure with atomic absorption spectrophotometer (FAAS) that to meet sample Cs (I) dense
Degree.
Result shows, 25 ° of C, flow velocity 1.0 mL min-1Time to record the equilibrium adsorption capacity of connect sample Cs (I) be 6.24
Mg/g, and balance is reached when T=120 min.Through comparing discovery, temperature is the lowest, and flow velocity is the least, and adsorption capacity is the biggest, and
Adsorption equilibrium required time is the longest.
Static selective absorption experiment: preparation Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), Cd (II) and mesh
Mark ion Cs () mixed liquor, the concentration of every kind of ion is 10 mg/L, takes the solution of the 25 above-mentioned preparations of mL in colorimetric cylinder
In, regulating pH value with watery hydrochloric acid or weak aqua ammonia is 6.0, add 20 mg Cs () ion imprinted polymer, test fluid is placed in 25
° C water-bath stands 12 h, is centrifugally separating to obtain supernatant, measure not with plasma emission spectrometer with atomic absorption spectrum
Adsorbed each concentration of metal ions.
Result shows, Cs (I)-IIP shows good recognition performance to Cs (I), and wherein Cs (I) is relative to competitive Adsorption
Ion Co (II), Sr (II), Ce (Ш), Pb (II), Ba (II), the selectivity factor of Cd (II) are respectively 4.67, and 6.83,
7.86,5.23,4.87,7.63, rather than trace adsorbent NIP shows very poor adsorptive selectivity to Cs (I), its corresponding selection
Property coefficient is respectively 0.54,0.97,1.56,2.01,1.09,0.93.
Described embodiment be the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment, not
In the case of deviating from the flesh and blood of the present invention, any conspicuously improved, the replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (8)
1. the preparation method of activity/controlled mesoporous material surface ion imprinted polymer, it is characterised in that include walking as follows
Rapid:
I, mesoporous material SBA-15 it is purified and activates；
II, the preparation of amino functional mesoporous material SBA-15: by above-mentioned SBA-15 and silane coupler in toluene in anaerobic
Under the conditions of reflux, product is scrubbed, be dried；
III, the preparation of the mesoporous material SBA-15 of grafted chain transfer agent: above-mentioned amino functional mesoporous material SBA-15 is added to
In the acetonitrile solution 1 of chain-transferring agent, ultrasonic rear ice bath stands, and adds the acetonitrile solution 2 of N, N-dicyclohexylcarbodiimide, in room
The lower reaction 10～20h of temperature, product is scrubbed, dry, and described chain-transferring agent is 2-(dodecyl trithiocarbonic acid ester group)-2-first
Base third (TTCA)；
IV, the preparation of ion imprinted polymer: by template ion, function monomer, crosslinking agent, above-mentioned grafted chain transfer agent mesoporous
Material SBA-15 stirs in methyl alcohol and acetonitrile mixture, adds initiator, in water-bath under oxygen free condition, uses EDTA
Solution washs and detects to metal ion washes clean, dries product.
2. method as claimed in claim 1, it is characterised in that described SBA-15 purifies and with activation method is: by SBA-15 in 80 DEG C
Lower standing aging 12～48h, is washed with deionized, the SBA-15 that backflow 18～72h must purify in ethanol；It is placed on dense
Degree is backflow 24h in 1.0～3.0mol/L hydrochloric acid solutions, is dried after being washed till neutrality.
3. method as claimed in claim 1, it is characterised in that silane coupler described in step II is 3-aminopropyl-triethoxy silicon
Alkane or 3-aminopropyl trimethoxysilane；Described toluene consumption is every 6.25～18.75g SBA-15 is scattered in 1L toluene, institute
Stating silane coupled agent concentration is 0.05～0.15mol/L；Described return time is 10～20h.
4. method as claimed in claim 1, it is characterised in that acetonitrile content described in step III is every 5.0～10.0g amino functional
Changing mesoporous material SBA-15 to be placed in 1L acetonitrile solution, the concentration of described chain-transferring agent is 0.01～0.03mol/L, described N, N-
Dicyclohexylcarbodiimide concentration in acetonitrile solution 2 is 0.04～0.08mol/L.
5. as claimed in claim 1 method, it is characterised in that template ion described in step IV for being provided by soluble metallic salt,
Described function monomer is methacrylic acid, and described crosslinking agent is ethylene glycol dimethacrylate or N, N '-methylene bisacrylamide
Acid amides, described initiator is azodiisobutyronitrile；
In described mixed liquor, methyl alcohol is 4:1 with the volume ratio of acetonitrile, and described template ion concentration is 5.0～15.0mmol/L, institute
The concentration stating function monomer and crosslinking agent is respectively 20.0～60.0mmol/L and 50.0～150.0mmol/L, described initiator
Consumption is every 50～the mesoporous material SBA-15 of 100mg grafted chain transfer agent adds 4～8mg initiators, described EDTA solution
Concentration is 0.1mol/L；Described bath temperature is 55～65 DEG C, and the water-bath time is 6～24h.
6. method as described in any one in claim 1-5, it is characterised in that described template ion be nickel, iron, caesium, copper,
Any one in strontium, mercury, cobalt, cadmium, manganese, zinc.
7. method as described in any one in claim 1-6 prepare activity/controlled mesoporous material surface ion trace gather
Compound.
8. activity/controlled mesoporous material surface ion imprinted polymer as claimed in claim 7 is corresponding in adsorption aqueous solution
The application of ion.
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| CN201410467787.2A CN104258826B (en) | 2014-09-15 | 2014-09-15 | A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application |
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| CN201410467787.2A CN104258826B (en) | 2014-09-15 | 2014-09-15 | A kind of activity/controlled mesoporous material surface ion imprinted polymer and preparation method and application |
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| CN104877090B (en) * | 2015-05-12 | 2017-08-04 | 江苏大学 | A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer |
| CN105148851B (en) * | 2015-09-28 | 2018-10-19 | 太原理工大学 | A kind of Preparation method and use of urea groups functionalization cadmium ion surface imprint adsorbent |
| CN105396555A (en) * | 2015-11-04 | 2016-03-16 | 安阳工学院 | Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions |
| CN105749879B (en) * | 2016-03-04 | 2018-08-10 | 江苏大学 | A kind of preparation method of duct filled-type molecular/ionic double site imprinted polymer |
| CN108246265B (en) * | 2017-11-22 | 2021-07-06 | 广东工业大学 | Synthesis of graphene oxide-mesoporous silicon surface hexavalent chromium imprinting material and method for applying same in water treatment |
| CN111707633B (en) * | 2020-06-24 | 2023-03-21 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Simultaneous Cu detection by organic-inorganic mesoporous hybrid material 2+ 、Co 2+ 、Ni 2+ Method of ionizing |
| CN112295549A (en) * | 2020-09-11 | 2021-02-02 | 中南大学 | Adsorbent for selectively separating gold and preparation method and application thereof |
| CN114345300B (en) * | 2022-01-07 | 2023-07-14 | 万华化学集团股份有限公司 | Adsorbent and preparation method thereof, and method for purifying cycloolefin polymer |
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| CN103623788A (en) * | 2013-11-22 | 2014-03-12 | 江苏大学 | Preparation method of magnetic mesoporous free radical controlled polymer ion printing adsorbing agent |
| CN103629393A (en) * | 2013-12-26 | 2014-03-12 | 大连深蓝泵业有限公司 | Conical surface sealing suction bottom valve matched with low-temperature immersed pump |
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| CN103433005A (en) * | 2013-08-26 | 2013-12-11 | 江苏大学 | Preparation method for triglycine functionalized mesoporous material surface imprinting adsorbent |
| CN103623788A (en) * | 2013-11-22 | 2014-03-12 | 江苏大学 | Preparation method of magnetic mesoporous free radical controlled polymer ion printing adsorbing agent |
| CN103629393A (en) * | 2013-12-26 | 2014-03-12 | 大连深蓝泵业有限公司 | Conical surface sealing suction bottom valve matched with low-temperature immersed pump |
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