CN103599757A - Preparation method of magnetic temperature-sensitive surface strontium ion blotting adsorbent - Google Patents
Preparation method of magnetic temperature-sensitive surface strontium ion blotting adsorbent Download PDFInfo
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- CN103599757A CN103599757A CN201310513288.8A CN201310513288A CN103599757A CN 103599757 A CN103599757 A CN 103599757A CN 201310513288 A CN201310513288 A CN 201310513288A CN 103599757 A CN103599757 A CN 103599757A
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Abstract
The invention relates to a preparation method of a magnetic temperature-sensitive surface strontium ion blotting adsorbent, and belongs to the technical field of the preparation of environmental function materials. The preparation method comprises the following steps: effectively combining Fe3O4 with aminated SBA-15 (PEI-SBA-15) Through a post grafting method to form Fe3O4@PEI-SBA-15, and carrying out vinyl modification of the Fe3O4@PEI-SBA-15 to obtain Fe3O4@PEI-SBA-15@MPS; and preparing the magnetic temperature-sensitive surface strontium ion blotting adsorbent by using the Fe3O4@PEI-SBA-15@MPS as a matrix and Sr (II) as a template. The adsorption performance of the adsorbent on the Sr (II) is investigated. The adsorbent has a substantial thermal stability, a substantial magnetic stability, a sensitive magnetic induction effect, a sensitive thermal induction effect, a substantial temperature-dependent reversible adsorption/release function, and an obvious Sr (II) identification performance.
Description
Technical field
The preparation method who the present invention relates to a kind of magnetic temp-sensitive type surface strontium ion trace adsorbent, belongs to environment functional material preparing technical field.
Background technology
Molecular imprinting is that preparation has the high molecular polymer synthetic technology of singleness identity (specific selectivity energy) to a certain specific template molecule (ion, molecule, compound, large biological molecule or microorganism), and its core is to prepare molecularly imprinted polymer (MIPs).MIPs inside is distributed with the trace hole of a large amount of template molecules, these holes and template molecule match to heavens at aspects such as space structure, binding sites, make molecularly imprinted polymer have special identification selection and good binding affinity to template molecule.When usining metal ion during directly as template molecule, can specifically be referred to as ion blotting technology.Surface ion engram technology is the trace method of stromal surface that the imprinted layer with recognition site is combined in, it preferably resolves some major defects that traditional molecular imprinting integral body also exists, as excessively dark in avtive spot embedding, the kinetic rate of mass transfer and charge transfer is slow, and the dynamic performance of adsorption-desorption is not good etc.With conventional host material SiO
2and TiO
2silicon titanium base micro/nano material etc. is compared, and silicon-based mesoporous material SBA-15 is with the aperture of its homogeneous, large specific area, compared with large pore volume and good finishing characteristic and be widely used as the host material of surface imprinted process.
What in recent years, intelligent trace system was prepared can become to the imprinted polymer of magnetic field, light source, temperature and pH value generation response effect the focus of research.Wherein, in order to realize the quick separation of adsorbent, tri-iron tetroxide (Fe
3o
4) nano particle is owing to having stronger superparamagnetism, magnetic surface imprinted polymers (MMIPs) that are used to prepare nucleocapsid structure more.Yet realize tri-iron tetroxide (Fe by Graft Method after simple
3o
4) combination of nano particle and mesoporous SBA-15, more not yet have report in the research that the surface imprinted modification of magnetic composite obtains magnetic blotting polymeric adsorbant.In addition, the temperature sensitive type imprinted polymer based on poly-N-isopropyl acrylamide (PNIPAM) is also a kind of typical intelligent trace system, and the intelligent molecularly imprinted polymer of temperature-responsive (being used for identification, the slowly-releasing of medicine) is also had to report more.Poly-N-isopropyl acrylamide (PNIPAAm) is a kind of typical temperature sensitive polymer, and its lowest critical solution temperature (LCST) is 32
onear C, and in the aqueous solution, there is special volume phase transition behavior: when temperature is during lower than LCST, imbibition; When temperature is during higher than LCST, syneresis, and this variation is reversible.Based on this, the molecular engram gel of temperature sensitive type has been reported, but its poor rigidity and adsorption capacity are low, has limited its practical application.Yet temperature sensitive type imprinting is based upon to the research that mesoporous material surface is especially based upon magnetic coupling mesoporous material surface not yet report.
Along with the utilization of continually developing of nuclear fuel material, in environment, be on the increase in the source of radioactive element.Wherein, the use amount of middle low-activity metallic element also increases greatly.Strontium is a kind of of middle low-activity metallic element, and it is as isotopic
90sr and
85sr has respectively the half-life that reaches 28 years and 64.8 days, and environmental and human health impacts is had to very large harm.
90sr can partly be attached in soil particle along with underground water is moved down into subsoil, and remaining is still stayed in underground water, enters after human body and other life entities, can long-term radiation marrow, impair one's health.Therefore the strontium ion of effectively removing in waste water has important Research Significance.Consider that synthetic magnetic temp-sensitive type surface strontium ion imprinted polymer has the single-minded selective recognition function of predetermined substance to strontium ion (Sr (II)), this provides a class new method for the middle low-activity Sr (II) in selective separation enrichment environmental sample.
Summary of the invention
The invention provides the preparation method of a kind of magnetic temp-sensitive type surface strontium ion trace adsorbent.
The technical solution used in the present invention is: first by Graft Method after simple, realized tri-iron tetroxide (Fe
3o
4) magnetic nano-particle and amination SBA-15(PEI-SBA-15) and effective combination (Fe
3o
4@PEI-SBA-15).Then utilize 3-(methacryloxypropyl) propyl trimethoxy silicane (MPS) to carry out vinyl modified to magnetic composite, obtain Fe
3o
4@[email protected] with Fe
3o
4@PEI-SBA-15@MPS is host material, Sr (II) is template, methyl-prop diluted acid (MAA) is function monomer, NIPA (NIPAM) is temperature sensitive type function monomer, N, N-methylene-bisacrylamide (BIS) is crosslinking agent, polyvinylpyrrolidone (PVP) is magnetic particle dispersant, 2,2'-azo diisobutyl amidine dihydrochloride (AIBA) is initator, prepare a kind of magnetic temp-sensitive type surface strontium ion trace adsorbent, and investigated the absorption property to Sr in the aqueous solution (II).
A preparation method for magnetic temp-sensitive type surface strontium ion trace adsorbent, carries out according to the following steps:
(1) magnetic core Fe
3o
4preparation
Take Iron(III) chloride hexahydrate (FeCl
36H
2o) be dissolved in ethylene glycol, wherein FeCl
36H
2the concentration of O in ethylene glycol is 16.88 ~ 33.75 g/L, is stirred to and forms yellow uniform solution.Then add respectively anhydrous sodium acetate (NaOAc) and polyethylene glycol (PEG10000), continue to transfer them to rapidly in polytetrafluoroethylene (PTFE) autoclave after stirring 30 min 200
ounder C, crystallization 8 ~ 10 h, are cooled to room temperature, ethanol washing, 60
oa dry night under C.
(2) synthesizing polyethyleneimine-modified SBA-15(PEI-SBA-15)
Take SBA-15 and γ-r-chloropropyl trimethoxyl silane (CP) and be dissolved in xylene solution, more slowly splash into deionized water, 80
ounder C condition, react 6 h, toluene wash is removed excessive CP, makes the SBA-15(CP-SBA-15 of surperficial chloropropylation).It is that in 20% polymine (PEI) aqueous solution, wherein the mass concentration of CP-SBA-15 in the PEI aqueous solution is 0.1 ~ 0.2 g/mL that the CP-SBA-15 making is added to mass fraction, 90
ounder C, continue reaction 6 h, with distilled water, fully wash products therefrom to neutral, suction filtration, makes the SBA-15(PEI-SBA-15 that PEI modifies after vacuum drying).
(3) Fe
3o
4synthetic and the surperficial modified by vinyl (Fe of@PEI-SBA-15
3o
4@PEI-SBA-15@MPS)
Take Fe
3o
4be scattered in n-hexane ultrasonic 10 min.Add the above-mentioned PEI-SBA-15 making to continue ultrasonic 30 min.Utilize magnet will be grafted with Fe
3o
4pEI-SBA-15(Fe
3o
4@PEI-SBA-15) carry out separation, with the abundant cleaning product of hexane solution to remove not grafting Fe
3o
4pEI-SBA-15, vacuum drying, makes Fe
3o
4@PEI-SBA-15;
Take above-mentioned synthetic Fe
3o
4@PEI-SBA-15 is scattered in the mixed solution of second alcohol and water, adds successively γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) and concentrated ammonia liquor (NH
3h
2o), 40
ounder C, stir 24 h, a large amount of ethanol washs to remove the MPS that does not participate in reaction, 60
oc vacuum drying, makes the Fe of surperficial modified by vinyl
3o
4@PEI-SBA-15, i.e. Fe
3o
4@PEI-SBA-15@MPS.
(4) preparation (Fe of magnetic temp-sensitive type strontium ion imprinted polymer
3o
4@PEI-SBA-15@IIPs)
Take strontium nitrate (Sr (NO
3)
2) be dissolved in the mixed solution of first alcohol and water, continue to add function monomer methacrylic acid (MAA), ultrasonic 10 min, logical N
210 min, seal 12 h that keep in Dark Place.In above-mentioned self assembly solution, add successively temperature sensitive monomer NIPA (NIPAM), crosslinking agent N, N-methylene-bisacrylamide (BIS).Be stirred to completely and continue to add Fe after dissolving
3o
4@PEI-SBA-15 MPS, containing the mixed solution of the first alcohol and water of 0.10g polyvinylpyrrolidone (PVP), wherein Fe
3o
4the concentration of@PEI-SBA-15@MPS in whole system is 1 ~ 2 g/L, 55
ological nitrogen 1 h that refluxes under C.Finally add 6 mg 2,2'-azo diisobutyl amidine dihydrochloride (AIBA), N
2lower 6 h that stir of protection.Reaction finish after, with 0.1 mol/L disodium ethylene diamine tetraacetate (EDTA) solution washing imprinted polymer 12 h with remove Sr (
), this process repeats 5 times.With atomic absorption spectrography (AAS) (FAAS) measure Sr in eluent (
) concentration with guarantee Sr (
) remove totally.
Wherein, the FeCl described in step (1)
36H
2the mass ratio of O, NaOAc and PEG10000 is: 1:2.67 ~ 5.33:0.74 ~ 1.48.
Wherein, the ratio of SBA-15, the CP described in step (2) and deionized water is 5g:7 ~ 14mL:1.4 ~ 2.0 mL.
Wherein, the Fe described in step (3)
3o
4, n-hexane and PEI-SBA-15 ratio be 0.1g:25mL:0.1 ~ 0.3g.
Wherein, the Fe described in step (3)
3o
4ratio in the mixed liquor of@PEI-SBA-15 and second alcohol and water is 0.3g:100mL, and in described mixed liquor, the volume ratio of second alcohol and water is 10:1.
Wherein, the Fe described in step (3)
3o
4@PEI-SBA-15, MPS and NH
3h
2the ratio of O is 0.3g:1.5 ~ 2.0mL:1.5 ~ 2.0mL.
Wherein, the template ion Sr described in step (4) (
) with the ratio of the mixed liquor of first alcohol and water being: 1mmol:10mL, in described mixed liquor, the volume ratio of first alcohol and water is 1:1.
Wherein, template ion Sr in the whole system described in step (4) (
), the ratio of the mixed liquor of MAA, NIPAM, BIS, methyl alcohol and water is 1mmol:2 ~ 6mmol:2mmol:2mmol:100mL, in described mixed liquor, the volume ratio of methyl alcohol and water is 1:1.
Wherein, in the mixed solution of the first alcohol and water containing 0.10g polyvinylpyrrolidone described in step (4), the volume ratio of first alcohol and water is 1:1.
The similar synthetic method of preparation method of the non-imprinted polymer (NIP) that the present invention is corresponding as above, but does not add Sr (NO
3)
2.
Prepared nonionic imprinted polymer (NIP) is as blank.
(5) prepared adsorbent is carried out to absorption property analytical test
1. Staticadsorption experiment:
By the Sr of 25 mL concentration known (
) solution joins in colorimetric cylinder, be placed in water bath with thermostatic control standing, initial concentration, pH, temperature, adsorption time and other metal ion disturbances of investigating adsorbent solution to trace adsorbent identification Sr (
) impact of ability.After absorption, by centrifugation, collect and obtain test fluid clear liquid at the middle and upper levels, the Sr not adsorbing (
) atomic absorption spectrophotometer for concentration (FAAS) and plasma emission spectrometer (ICP) measure, and according to result calculate adsorption capacity (
q e, mg/g).
Wherein
c 0(mg/L) and
c e(mg/L) be respectively absorption before and after Sr (
) concentration,
w(g) be adsorbent consumption,
v(L) be test fluid volume.
2. selective absorption test
Selection Mg (
), Ca (
), Pb (
), Cd (
) be competitive Adsorption ion, be configured to respectively four kinds of ions and Sr (
) mixed solution, the concentration of every kind of ion is all 5 mg/ L.Get the solution that 25 mL configure and join in colorimetric cylinder, add respectively 20 mg traces and non-trace adsorbent, test fluid is placed in the water-bath of 35 ° of C to standing 12.0 h respectively.After time of repose completes, centrifugation obtains supernatant, and the plasma emission spectrometer for concentration (ICP) of the various competitive Adsorption substrates of absorption is not measured.
Beneficial effect of the present invention is:
A kind of magnetic temp-sensitive type surface strontium ion trace adsorbent prepared by the present invention has significant heat and magnetic stability, good Magnetic Isolation performance and responsive thermoinduction effect, can vary with temperature and show reversible adsorption/release function, Sr (II) is had to adsorption capacity large, selective high, separating effect is remarkable, reuses advantage often.This provides a class new method for the middle low-activity Sr (II) in selective separation enrichment environmental sample.
Accompanying drawing explanation
Fig. 1: Fig. 1 (a) and Fig. 1 (b) are respectively Fe
3o
4and Fe
3o
4the scanning electron microscope (SEM) photograph of@PEI-SBA-15@IIPs; Fig. 1 (c) and Fig. 1 (d) are respectively Fe
3o
4and Fe
3o
4the transmission electron microscope picture of@PEI-SBA-15@IIPs; Fig. 1 (e) is magnetic core Fe after trace
3o
4the amplification transmission electron microscope picture on surface.
From Fig. 1 (a) and Fig. 1 (b), Fe
3o
4magnetic nano-particle be grafted on well at SBA-15 surface integral, arrange after the surface of PEI-SBA-15 and trace comparatively regular.Fig. 1 (c), Fig. 1 (d) and Fig. 1 (e) have illustrated that imprinted polymer thin layer is grafted to the surface of magnetic mesoporous silicon SBA-15 effectively preferably.
The specific embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
(1) magnetic core Fe
3o
4preparation
Take 0.675 g FeCl
36H
2o is dissolved in 40 mL ethylene glycol, is stirred to and forms yellow uniform solution.In above-mentioned solution, add successively 3.6 g anhydrous sodium acetates (NaOAc) and 1.0 g polyethylene glycol (PEG10000), continue to transfer them to rapidly in 50 mL polytetrafluoroethylene (PTFE) autoclaves after stirring 30 min 200
ounder C, crystallization 8 h, are cooled to room temperature, ethanol washing, 60
oa dry night under C.
(2) PEI-SBA-15's is synthetic
Take 5.00 g SBA-15 and 7 mL γ-r-chloropropyl trimethoxyl silanes (CP) in 40 mL xylene solutions, slowly splash into 1.4 mL deionized waters, 80
ounder C condition, react 6 h, toluene fully washs to remove excessive CP, makes the SBA-15 (CP-SBA-15) of surperficial chloropropylation.By the CP-SBA-15(5.00 g making) add in polymine (PEI) aqueous solution that 25 mL mass fractions are 20% 90
ounder C, continue reaction 6 h, fully wash products therefrom cause neutrality with distilled water, suction filtration, makes the SBA-15(PEI-SBA-15 of PEI modification after vacuum drying).
(3) Fe
3o
4synthetic and the surperficial modified by vinyl (Fe of@PEI-SBA-15
3o
4@PEI-SBA-15@MPS)
By the synthetic Fe of 0.10 g
3o
4be scattered in 25mL n-hexane ultrasonic 10 min.Add the above-mentioned PEI-SBA-15 making (0.10g), continue ultrasonic 30min.Utilize magnet will be grafted with Fe
3o
4pEI-SBA-15(Fe
3o
4@PEI-SBA-15) carry out separation, with the abundant cleaning product of hexane solution to remove not grafting Fe
3o
4pEI-SBA-15, vacuum drying is standby.
Take 0.30g Fe
3o
4@PEI-SBA-15 is scattered in the mixed solution (wherein the volume ratio of second alcohol and water is 10:1) of 100mL second alcohol and water, adds successively 1.5 mL γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) and 1.5 mL NH
3h
2o, 40
ounder C, stir 24 h, a large amount of ethanol washs to remove the MPS that does not participate in reaction, 60
oc vacuum drying.
(4) preparation (Fe of magnetic temp-sensitive type strontium ion imprinted polymer
3o
4@PEI-SBA-15@IIPs)
Get 0.22 g Sr (NO
3)
2be dissolved in the mixed solution (wherein the volume ratio of first alcohol and water is 1:1) of 10 mL first alcohol and waters, continue to add 0.18 mL methacrylic acid (MAA), ultrasonic 10 min, logical N
210 min, seal 12 h that keep in Dark Place.In above-mentioned self assembly solution, add successively 0.23 g NIPA (NIPAM), 0.31 g N, N-methylene-bisacrylamide (BIS), is stirred to completely and continues to add 0.10 g Fe after dissolving
3o
4@PEI-SBA-15 MPS, containing mixed solution (wherein the volume ratio of first alcohol and water is 1:1) 90 mL of the first alcohol and water of 0.10 g polyvinylpyrrolidone (PVP), 55
ological nitrogen 1 h that refluxes under C.Finally add 6 mg 2,2'-azo diisobutyl amidine dihydrochloride (AIBA), N
2lower 6.0 h that stir of protection.Reaction finish after, with 0.1 mol/L disodium ethylene diamine tetraacetate (EDTA) solution washing imprinted polymer 12 h with remove Sr (
), this process repeats 5 times.With atomic absorption spectrography (AAS) (FAAS) measure Sr in eluent (
) concentration with guarantee Sr (
) remove totally.Above-mentioned same method, does not add Sr (NO
3)
2prepare nonionic imprinted polymer (NIP) as blank.
(4) adsorption test
Getting Sr (II) solution that 25 mL initial concentrations are respectively 3,5,8,15,30,50,100,150,200,300,400,450 and 500 mg/L joins in 25 mL colorimetric cylinders, with watery hydrochloric acid or weak aqua ammonia, regulating pH value is 6.5, add respectively 10 mg traces and non-trace adsorbent, three groups of test fluid are placed on respectively in the water-bath of 25,35,45 ° of C after standing 12 h, magnet separation obtains supernatant liquor, the Sr not being adsorbed in supernatant liquor (II) concentration Atomic Absorption Spectrometry, and calculate adsorption capacity according to result.Result shows Fe
3o
4the saturated extent of adsorption of@PEI-SBA-15@IIPs under 35 ° of C is 62.37 mg/g, far above 27.21 mg/g of non-trace adsorbent.
(5) selectively experiment
Sr (
) and Mg (
), Ca (
), Pb (
), Cd (
) competitive Adsorption of the binary system that mixes, get concentration that 25 mL configure and be 5 mg/L Sr (
)/M (
) mixed solution joins in colorimetric cylinder, by watery hydrochloric acid or weak aqua ammonia adjusting pH value, is 6.5, adds respectively 20 mg Fe
3o
4@PEI-SBA-15@IIPs and NIP.Test fluid is placed on to standing 12 h in the water-bath of 35 ° of C.After standing completing, magnet separation obtains supernatant liquor, the Sr not adsorbed in supernatant liquor (II) and other competitive Adsorption ion M (
) concentration with ICP, measure, according to result, calculate adsorption capacity.Result shows Fe
3o
4@PEI-SBA-15@IIPs shows good recognition performance to Sr (II), wherein Sr (II) with respect to competitive Adsorption ION Mg (
), Ca (
), Pb (
), Cd (
) selectivity factor be respectively 10.28,6.92,7.36 and 4.19, but not trace adsorbent NIP shows very poor adsorptive selectivity to Sr (II).
embodiment 2:
(1) magnetic core Fe
3o
4preparation
Take 1.35 g FeCl
36H
2o is dissolved in 40 mL ethylene glycol, is stirred to and forms yellow uniform solution.In above-mentioned solution, add successively 3.6 g anhydrous sodium acetates (NaOAc) and 1.0 g polyethylene glycol (PEG10000), continue to transfer them to rapidly in 50 mL polytetrafluoroethylene (PTFE) autoclaves after stirring 30 min 200
ounder C, crystallization 10 h, are cooled to room temperature, ethanol washing, 60
oa dry night under C.
(2) PEI-SBA-15's is synthetic
Take 5.00 g SBA-15 and 14 mL γ-r-chloropropyl trimethoxyl silanes (CP) in 40 mL xylene solutions, slowly splash into 2.0 mL deionized waters, 80
ounder C condition, react 6 h, toluene fully washs to remove excessive CP, makes the SBA-15 (CP-SBA-15) of surperficial chloropropylation.By the CP-SBA-15(5.00 g making) add in polymine (PEI) aqueous solution that 50 mL mass fractions are 20% 90
ounder C, continue reaction 6 h, fully wash products therefrom cause neutrality with distilled water, suction filtration, makes the SBA-15(PEI-SBA-15 of PEI modification after vacuum drying).
(3) Fe
3o
4synthetic and the surperficial modified by vinyl (Fe of@PEI-SBA-15
3o
4@PEI-SBA-15@MPS)
By the synthetic Fe of 0.10 g
3o
4be scattered in 25 mL n-hexanes ultrasonic 10 min.Add the above-mentioned PEI-SBA-15(0.30 g making), continue ultrasonic 30 min.Utilize magnet will be grafted with Fe
3o
4pEI-SBA-15(Fe
3o
4@PEI-SBA-15) carry out separation, with the abundant cleaning product of hexane solution to remove not grafting Fe
3o
4pEI-SBA-15, vacuum drying is standby.
Take 0.30 g Fe
3o
4@PEI-SBA-15 is scattered in the mixed solution (wherein the volume ratio of second alcohol and water is 10:1) of 100 mL second alcohol and waters, adds successively 2.0 mL γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) and 2.0 mL NH
3h
2o, 40
ounder C, stir 24 h, a large amount of ethanol washs to remove the MPS that does not participate in reaction, 60
oc vacuum drying.
(4) preparation (Fe of magnetic temp-sensitive type strontium ion imprinted polymer
3o
4@PEI-SBA-15@IIPs)
Get 0.22 g Sr (NO
3)
2be dissolved in the mixed solution (wherein the volume ratio of first alcohol and water is 1:1) of 10 mL first alcohol and waters, continue to add 0.52 mL methacrylic acid (MAA), ultrasonic 10 min, logical N
210 min, seal 12 h that keep in Dark Place.In above-mentioned self assembly solution, add successively 0.23 g NIPA (NIPAM), 0.31 g N, N-methylene-bisacrylamide (BIS), is stirred to completely and continues to add 0.20 g Fe after dissolving
3o
4@PEI-SBA-15 MPS, containing mixed solution (wherein the volume ratio of first alcohol and water is 1:1) 90 mL of the first alcohol and water of 0.10 g polyvinylpyrrolidone (PVP), 55
ological nitrogen 1 h that refluxes under C.Finally add 6 mg 2,2'-azo diisobutyl amidine dihydrochloride (AIBA), N
2lower 6.0 h that stir of protection.Reaction finish after, with 0.1 mol/L disodium ethylene diamine tetraacetate (EDTA) solution washing imprinted polymer 12 h with remove Sr (
), this process repeats 5 times.With atomic absorption spectrography (AAS) (FAAS) measure Sr in eluent (
) concentration with guarantee Sr (
) remove totally.Same method, does not add Sr (NO
3)
2prepare nonionic imprinted polymer (NIP) as blank.
(4) adsorption test
Getting Sr (II) solution that 25 mL initial concentrations are respectively 3,5,8,15,30,50,100,150,200,300,400,450 and 500 mg/L joins in 25 mL colorimetric cylinders, with watery hydrochloric acid or weak aqua ammonia, regulating pH value is 6.5, add respectively 10 mg traces and non-trace adsorbent, three groups of test fluid are placed on respectively in the water-bath of 25,35,45 ° of C after standing 12 h, magnet separation obtains supernatant liquor, the Sr not being adsorbed in supernatant liquor (II) concentration Atomic Absorption Spectrometry, and calculate adsorption capacity according to result.Result shows Fe
3o
4the saturated extent of adsorption of@PEI-SBA-15@IIPs under 35 ° of C is 89.73 mg/g, far above 33.52 mg/g of non-trace adsorbent.
(5) selectively experiment
Sr (
) and Mg (
), Ca (
), Pb (
), Cd (
) competitive Adsorption of the binary system that mixes, get concentration that 25 mL configure and be 5 mg/L Sr (
)/M (
) mixed solution joins in colorimetric cylinder, by watery hydrochloric acid or weak aqua ammonia adjusting pH value, is 6.5, adds respectively 20 mg Fe
3o
4@PEI-SBA-15@IIPs and NIP.Test fluid is placed on to standing 12 h in the water-bath of 35 ° of C.After time of repose completes, magnet separation obtains supernatant liquor, the Sr not being adsorbed in supernatant liquor (II) and other competitive Adsorption ion M (
) concentration with ICP, measure, according to result, calculate adsorption capacity.Result shows Fe
3o
4@PEI-SBA-15@IIPs shows good recognition performance to Sr (II), wherein Sr (II) with respect to competitive Adsorption ION Mg (
), Ca (
), Pb (
), Cd (
) selectivity factor be respectively 14.25,7.37,9.39 and 3.65, but not trace adsorbent NIP shows very poor adsorptive selectivity to Sr (II).
Claims (9)
1. a preparation method for magnetic temp-sensitive type surface strontium ion trace adsorbent, is characterized in that carrying out according to the following steps:
(1) magnetic core Fe
3o
4preparation
Take FeCl
36H
2o is dissolved in ethylene glycol, wherein FeCl
36H
2the concentration of O in ethylene glycol is 16.88 ~ 33.75 g/L, is stirred to and forms yellow uniform solution; Then add respectively anhydrous sodium acetate and polyethylene glycol, continue to transfer them to rapidly in polytetrafluoroethylene (PTFE) autoclave after stirring 30 min 200
ounder C, crystallization 8 ~ 10 h, are cooled to room temperature, ethanol washing, 60
oa dry night under C;
(2) polyethyleneimine-modified SBA-15's is synthetic
Take SBA-15 and γ-r-chloropropyl trimethoxyl silane is dissolved in xylene solution, more slowly splash into deionized water, 80
ounder C condition, react 6h, toluene wash is removed excessive γ-r-chloropropyl trimethoxyl silane, makes the SBA-15 of surperficial chloropropylation; It is that in 20% polyethyleneimine: amine aqueous solution, wherein the mass concentration of the SBA-15 of surperficial chloropropylation in polyethyleneimine: amine aqueous solution is 0.1 ~ 0.2 g/mL that the SBA-15 of the surperficial chloropropylation making is added to mass fraction, 90
ounder C, continue reaction 6h, with distilled water, fully wash products therefrom to neutral, suction filtration, makes the SBA-15 of polyethyleneimine-modified, i.e. PEI-SBA-15 after vacuum drying;
(3) Fe
3o
4synthetic and the surperficial modified by vinyl of@PEI-SBA-15
Take Fe
3o
4be scattered in n-hexane ultrasonic 10min; Add the above-mentioned PEI-SBA-15 making to continue ultrasonic 30 min; Utilize magnet will be grafted with Fe
3o
4pEI-SBA-15 carry out separation, with the abundant cleaning product of hexane solution to remove not grafting Fe
3o
4pEI-SBA-15, vacuum drying, makes Fe
3o
4@PEI-SBA-15;
Take above-mentioned synthetic Fe
3o
4@PEI-SBA-15 is scattered in the mixed solution of second alcohol and water, adds successively γ-(methacryloxypropyl) propyl trimethoxy silicane and concentrated ammonia liquor, 40
ounder C, stir 24 h, a large amount of ethanol washs to remove γ-(methacryloxypropyl) propyl trimethoxy silicane of not participating in reaction, 60
oc vacuum drying, makes the Fe of surperficial modified by vinyl
3o
4@PEI-SBA-15, i.e. Fe
3o
4@PEI-SBA-15@MPS;
(4) preparation of magnetic temp-sensitive type strontium ion imprinted polymer
Take in the mixed solution that strontium nitrate is dissolved in first alcohol and water, continue to add function monomer methacrylic acid, ultrasonic 10 min, logical N
210 min, seal 12 h that keep in Dark Place; In above-mentioned self assembly solution, add successively temperature sensitive monomer NIPA, crosslinking agent N, N-methylene-bisacrylamide; Be stirred to completely and continue to add Fe after dissolving
3o
4@PEI-SBA-15 MPS, containing the mixed solution of the first alcohol and water of 0.10g polyvinylpyrrolidone, wherein Fe
3o
4the concentration of@PEI-SBA-15@MPS in whole system is 1 ~ 2 g/L, 55
ological nitrogen 1 h that refluxes under C; Finally add 6 mg 2,2'-azo diisobutyl amidine dihydrochloride, N
2lower 6 h that stir of protection; After reaction finishes, with 0.1 mol/L disodium ethylene diamine tetra-acetic acid solution wash imprinted polymer 12 h with remove Sr (
), this process repeats 5 times; With Sr in Atomic Absorption Spectrometry amount eluent (
) concentration with guarantee Sr (
) remove totally.
2. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that the FeCl described in step (1)
36H
2the mass ratio of O, anhydrous sodium acetate and polyethylene glycol is: 1:2.67 ~ 5.33:0.74 ~ 1.48.
3. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, it is characterized in that, the ratio of SBA-15, γ-r-chloropropyl trimethoxyl silane and the deionized water described in step (2) is 5g:7 ~ 14mL:1.4 ~ 2.0 mL.
4. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that the Fe described in step (3)
3o
4, n-hexane and PEI-SBA-15 ratio be 0.1g:25mL:0.1 ~ 0.3g.
5. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that the Fe described in step (3)
3o
4the ratio of the mixed liquor of@PEI-SBA-15 and second alcohol and water is 0.3g:100mL, and in described mixed liquor, the volume ratio of second alcohol and water is 10:1.
6. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that the Fe described in step (3)
3o
4the ratio of@PEI-SBA-15, γ-(methacryloxypropyl) propyl trimethoxy silicane and concentrated ammonia liquor is 0.3g:1.5 ~ 2.0mL:1.5 ~ 2.0mL.
7. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that, the template ion Sr described in step (4) (
) with the ratio of the mixed liquor of first alcohol and water being: 1mmol:10mL, in described mixed liquor, the volume ratio of first alcohol and water is 1:1.
8. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, is characterized in that, template ion Sr in the whole system described in step (4) (
), methacrylic acid, NIPA, N, the ratio of the mixed liquor of N-methylene-bisacrylamide, methyl alcohol and water is 1mmol:2 ~ 6mmol:2mmol:2mmol:100mL, in described mixed liquor, the volume ratio of methyl alcohol and water is 1:1.
9. the preparation method of a kind of magnetic temp-sensitive type according to claim 1 surface strontium ion trace adsorbent, it is characterized in that, in the mixed solution of the first alcohol and water containing 0.10g polyvinylpyrrolidone described in step (4), the volume ratio of first alcohol and water is 1:1.
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| CN107551987A (en) * | 2017-10-19 | 2018-01-09 | 兰州大学 | A kind of magnetic adsorbent and its production and use |
| WO2018021974A1 (en) * | 2016-07-28 | 2018-02-01 | Nanyang Technological University | Composite material, its manufacture and use in gas purification |
| CN112295549A (en) * | 2020-09-11 | 2021-02-02 | 中南大学 | Adsorbent for selectively separating gold and preparation method and application thereof |
| CN113491997A (en) * | 2021-06-30 | 2021-10-12 | 北京碧水源膜科技有限公司 | Lead ion sieve Na-TiAlSi-O, preparation method and application thereof |
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| CN103055823A (en) * | 2012-12-14 | 2013-04-24 | 江苏大学 | Preparation method of surface print adsorbent of yeast template hollow silica-based material for adsorbing and separating strontium ions and application thereof |
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|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| WO2018021974A1 (en) * | 2016-07-28 | 2018-02-01 | Nanyang Technological University | Composite material, its manufacture and use in gas purification |
| CN109310981A (en) * | 2016-07-28 | 2019-02-05 | 南洋理工大学 | Composite material, its preparation and gas purification purposes |
| US11247190B2 (en) | 2016-07-28 | 2022-02-15 | Nanyang Technological University | Composite material, its manufacture and use in gas purification |
| CN107551987A (en) * | 2017-10-19 | 2018-01-09 | 兰州大学 | A kind of magnetic adsorbent and its production and use |
| CN112295549A (en) * | 2020-09-11 | 2021-02-02 | 中南大学 | Adsorbent for selectively separating gold and preparation method and application thereof |
| CN113491997A (en) * | 2021-06-30 | 2021-10-12 | 北京碧水源膜科技有限公司 | Lead ion sieve Na-TiAlSi-O, preparation method and application thereof |
| CN113491997B (en) * | 2021-06-30 | 2023-03-21 | 北京碧水源膜科技有限公司 | Lead ion sieve Na-TiAlSi-O, preparation method and application thereof |
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