CN103638911B - The preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube - Google Patents
The preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube Download PDFInfo
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Abstract
The present invention relates to the preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube, belong to technical field of environment function material preparation.First the present invention has prepared magnetic carbon nano-tube by wet-impregnation techniques, then utilizes 3-(methacryloxypropyl) propyl trimethoxy silicane to carry out vinyl modified to MCNTs.Subsequently with 2,4,5-trichlorophenol, 2,4,6,-T is template molecule, acrylamide is function monomer, NIPA is temperature sensitive type monomer, and ethylene glycol bisthioglycolate (methacrylic acid) ester is crosslinking agent, 2,2 ˊ-azodiisobutyronitrile is initator, has prepared TMNIPs by free radical heat polymerization process.Advantage is: avoiding segment template molecule dark and cannot the problem of wash-out because embedding, improve adsorption capacity and adsorption dynamics adsorption kinetics performance; Magnetic carbon nano-tube prepared by wet-impregnation techniques can effectively prevent magnetic particle from revealing, and can accelerate separating effect.
Description
Technical field
The present invention relates to the preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube, belong to technical field of environment function material preparation.
Background technology
Molecular imprinting is the method that preparation has molecule distinguishability polymer.First the method forms complex by the covalently or non-covalently key between function monomer and template molecule, then the complex immobilization that crosslinking agent and initator will be formed is added, finally by some extraction means by template molecule elution, in the molecularly imprinted polymer (MIPs) of acquisition, just leave binding site template molecule to single-minded recognition reaction.Surface imprinted technology is passed through imprinted sites grafting or is coated on solid material surface, can significantly improve MIPs to the adsorption capacity of template molecule and adsorption dynamics adsorption kinetics performance.CNT (CNTs), as one of the new material of 21 century, has that specific area is large, good mechanical property and advantages such as preparation method is simple, environmental protection, is desirable surface imprinted carrier material.
In recent years, in order to improve adsorption separation efficiency, magnetic carrier isolation technics is employed in molecular imprinting.As tri-iron tetroxide (Fe
3o
4) nano particle has stronger superparamagnetism, the magnetic blotting polymer (MMIPs) obtained after its Surface coating imprinted polymer can realize outside magnetic field auxiliary under optionally target contaminant is separated rapidly with mother liquor.Meanwhile, for the ease of controlling adsorption process, the temperature sensitive polymer based on poly-N-isopropyl acrylamide (PNIPAM) has also been introduced into molecular engram system, prepares temperature sensitive imprinted polymer (TMIPs).PNIPAM is owing to its macromolecule side chain having hydrophilic amide groups one CONH mono-and hydrophobic isopropyl one CH (CH simultaneously
3)
2, near 32 DEG C, there will be volumetric expansion-contraction, thus occur to change hydrophobic phase in version into by hydrophily.
Chlorophenol (CP) is typical Some Persistent Organic Pollutants, and the main source of 2,4,5-trichlorophenol, 2,4,6,-Ts (2,4,5-TCP) is wherein timber preservative, pesticide and bactericide.The bio-toxicity lasting due to it and cumulative bad, TCP is listed in " persistence, bioaccumulation, toxicity " list of chemicals by U.S. environment protection tissue.For this reason, in Selective recognition and isolating environment water body, TCP is necessary.
Summary of the invention
First the present invention has prepared magnetic carbon nano-tube (MCNTs) by wet-impregnation techniques, then utilizes 3-(methacryloxypropyl) propyl trimethoxy silicane (MPS) to carry out vinyl modified to MCNTs.Subsequently with obtained vinyl modified magnetic carbon nano-tube for host material, 2, 4, 5-trichlorophenol, 2,4,6,-T (2, 4, 5-TCP) be template molecule, acrylamide (AM) is function monomer, NIPA (NIPAM) is temperature sensitive type monomer, ethylene glycol bisthioglycolate (methacrylic acid) ester (EGDMA) is crosslinking agent, 2, 2'-azodiisobutyronitrile (AIBN) is initator, the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube (TMNIPs) has been prepared by free radical heat polymerization process, characterize magnetic, the physicochemical properties such as pattern, and examine TMNIPs Selective recognition and release 2, 4, the ability of 5-TCP.
The technical solution used in the present invention is:
(1) magnetic carbon nano-tube particle (MCNTs) is prepared:
By CNT, Fe (NO
3)
39H
2o and absolute ethyl alcohol are according to (0.22-0.25): (0.1-0.2): the ratio mixing also ultrasonic disperse 1.0-1.5h of (10-12) (g/g/ml).Subsequently, above-mentioned dispersion liquid heats 12-14h to obtain dry powder at 60-65 DEG C.Then, the dried powder of acquisition put into porcelain boat and proceeds to tube furnace, at propionic acid steam protection and 80-85 DEG C, heating 15-18h, powder continues at nitrogen protection and 260-280 DEG C, to heat 2.0-2.5h in tube furnace subsequently.Finally, the black product of cooling to proceed in beaker and with distilled water and absolute ethanol washing 3 times, washing afterproduct Nd-Fe-B permanent magnet reclaims, and is placed in vacuum drying chamber 55-60 DEG C of dry 6.0-8.0h, obtains magnetic carbon nano-tube particle.
(2) vinyl modified of magnetic carbon nano-tube particle:
Prepare the dispersion liquid of magnetic carbon nano-tube particle in the ratio of 165-180ml ethanol and water mixed liquid according to every gram of magnetic carbon nano-tube particle dispersion, and at room temperature stir 0.5-1.0h, wherein in ethanol and water mixed liquid, the volume ratio of second alcohol and water is (8-10): 1.Subsequently, add the ratio of 3.5-5.0mlMPS according to every gram of magnetic carbon nano-tube particle, in the dispersion liquid of above-mentioned magnetic carbon nano-tube particle, add MPS, the mixed solution simultaneously obtained stirs 24h at 40-45 DEG C.Then, the magnetic carbon nano-tube particle of vinyl modified Nd-Fe-B permanent magnet reclaims, and with distilled water and absolute ethanol washing 3 times.After washing, the magnetic carbon nano-tube particle of vinyl modified is placed in vacuum drying chamber 50-55 DEG C of dry 5.0-6.0h.
(3) preparation of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube:
1) by 2,4,5-TCP, temperature sensitive monomer NIPAM, function monomer AM are 1.0:(3.5-4.0 in molar ratio): the ratio of (1.4-1.8) is dissolved in methyl-sulfoxide (DMSO), wherein the consumption of DMSO is every mM 2,4,5-TCP uses 10-15mlDMSO.The mixed solution ultrasonic disperse 1.0-1.5h obtained, strengthens the pre-assembled of template molecule and function monomer, the pre-assembled solution of ultrasonic rear acquisition.
2) magnetic carbon nano-tube of oleic acid and vinyl modified is placed in there-necked flask mechanical agitation 1.0-1.5h, the ratio of modified magnetic CNT and oleic acid is (0.25-0.5): (2.0-4.0) (g/ml), obtains the modified magnetic CNT that oleic acid infiltrates after stirring.Then according to every mM 2,4,5-TCP adds the ratio of 1.46-1.85mlEGDMA, crosslinking agent EGDMA is added in the modified magnetic CNT that oleic acid infiltrates, continue the pre-assembled solution (wherein every mM 2 added in step 1) subsequently wherein, 4,5-TCP need add the pre-assembled solution of DMSO containing 10-15ml), continue to stir 30-60min and obtain pre-polymer solution.
3) according to every mM 2,4,5-TCP adds the ratio (in the aqueous solution of DMSO, the volume ratio of methyl-sulfoxide and water is 9:1) of 0.4-0.6g polyvinylpyrrolidone (PVP) and the 100-120mlDMSO aqueous solution, add the aqueous solution of PVP and DMSO in the pre-polymer solution prepared in step 2, the mixed solution obtained stirs 15-30min; Then in mixed solution, logical nitrogen gets rid of oxygen 10-15min, then in mixed solution according to every mM 2,4,5-TCP adds initiator A IBN0.1-0.3g, and control temperature reacts 6.0-9.0h at 50-55 DEG C, then temperature obtains the surface imprinted temperature-sensitivadsorbent adsorbent of product magnetic carbon nano-tube (TMMIPs) after rising to 70-80 DEG C of polymerization 18-20h.
4) the surface imprinted temperature-sensitivadsorbent adsorbent of product magnetic carbon nano-tube (TMMIPs) agent Nd-Fe-B permanent magnet is collected, 3 times are washed with absolute ethyl alcohol and distilled water, be finally extract 80 DEG C of soxhlet extractions with the mixed liquor that the volume ratio of methyl alcohol and acetic acid is 95:5, until can't detect 2 in eluent, 4,5-TCP, then vacuum drying at 50-60 DEG C.
5) in order to carry out comparative study, prepared the non-trace temperature-sensitivadsorbent adsorbent (TMNIPs) in magnetic carbon nano-tube surface in this work simultaneously, preparation method and the TMMIPs of TMNIPs are similar, the consumption of agents useful for same adds with reference to the consumption during TMMIPs that preparation is corresponding, just do not add 2,4,5-TCP.
Technological merit of the present invention: the coupling of the advantage of surface imprinted technology, magnetic carrier method and temperature sensitive type poly compound has been prepared the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube by this product.That the use of surface molecule print technology avoids segment template molecule is dark and cannot the problem of wash-out because embedding, and available protecting identification point, improves adsorption capacity and adsorption dynamics adsorption kinetics performance; The magnetic carbon nano-tube prepared by wet-impregnation techniques can effectively prevent magnetic particle from revealing, and enhances the ability of acid resistance corrosion, simultaneously as effective magnetic carrier, can accelerate separating effect; The utilization of temperature sensitive type poly compound can regulate absorption and the dispose procedure of adsorbent by temperature switch.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of magnetic carbon nano-tube (MCNTs) and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube (TMMIPs) in embodiment 1, can find the Fe in MCNTs cavity from figure
3o
4be about 20nm, trace polymer layer temperature sensitive in TMMIPs is about 25nm.
Fig. 2 is embodiment 1 magnetic carbon nano-tube, the magnetic carbon nano-tube of vinyl modified and the thermogravimetric curve figure of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube.Can find from figure, the vinyl modified in the magnetic carbon nano-tube of vinyl modified accounts for 11% of weight, and in the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube, magnetic carbon nano-tube accounts for 11% of weight.
Fig. 3 is the hysteresis graph of magnetic carbon nano-tube and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube in embodiment 1.Can find that from figure the saturated magnetic intensity of magnetic carbon nano-tube and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube is respectively 3.4emu/g and 1.4emu/g, there is desirable Magnetic Isolation effect.
Fig. 4 is the absorbance figure (determined wavelength is 542nm) in embodiment 1 under the surface imprinted temperature-sensitivadsorbent adsorbent different temperatures of magnetic carbon nano-tube.The minimum critical-temperature (LCST) of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube is about 36.2 as we know from the figure
oc.
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further described.
Embodiment 1:
1, a preparation method for the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube, is characterized in that carrying out according to following step:
(1) magnetic carbon nano-tube particle (MCNTs) is prepared
0.22g CNT and 0.1gFe (NO
3)
39H
2o to be dissolved in 10ml ethylene glycol and ultrasonic disperse 1.0h.Dispersion liquid heats 12h to obtain dry powder at 60 DEG C subsequently.Then, the dried powder of acquisition put into porcelain boat and proceeds to tube furnace, at propionic acid steam protection and 80 DEG C, heating 15h, powder continues at nitrogen protection and 260 DEG C, to heat 2.0h in tube furnace subsequently.Finally, the black product of cooling to proceed in beaker and with distilled water and absolute ethanol washing 3 times, washing afterproduct Nd-Fe-B permanent magnet reclaims, and is placed in vacuum drying chamber 55 DEG C of dry 6.0h, obtains magnetic carbon nano-tube particle.
(2) vinyl modified of magnetic carbon nano-tube particle:
Get 1.0g magnetic carbon nano-tube and be scattered in the dispersion liquid preparing magnetic carbon nano-tube in 165ml ethanol and water mixed liquid, and at room temperature stir 0.5h, wherein in ethanol and water mixed liquid, the volume ratio of second alcohol and water is (8:1).Subsequently, in the dispersion liquid of magnetic carbon nano-tube, add 3.5mlMPS, the mixed solution of acquisition stirs 24h at 40 DEG C.Then, the magnetic carbon nano-tube particle of vinyl modified Nd-Fe-B permanent magnet reclaims, and with distilled water and absolute ethanol washing 3 times.After washing, the magnetic carbon nano-tube particle of vinyl modified is placed in vacuum drying chamber 50 DEG C of dry 5.0h.
(3) preparation of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube:
1) by 1.0mmol2,4,5-TCP, 4.0mmol temperature sensitive monomer NIPAM, 1.8mmol function monomer AM dissolves in 10ml methyl-sulfoxide (DMSO).The mixed solution ultrasonic disperse 1.0h obtained, strengthens the pre-assembled of template molecule and function monomer, the pre-assembled solution of ultrasonic rear acquisition.
2) magnetic carbon nano-tube of 0.25g vinyl modified and 2.0ml oleic acid are placed in there-necked flask mechanical agitation 1.0h, mix the modified magnetic CNT that rear acquisition oleic acid infiltrates.Then in the modified magnetic CNT of oleic acid infiltration, add crosslinking agent EGDMA1.46ml, continue wherein subsequently to add above-mentioned pre-assembled solution, continue to stir 30min and obtain pre-polymer solution.
3) in above-mentioned pre-polymer solution, add the aqueous solution (in the aqueous solution of DMSO, the volume ratio of methyl-sulfoxide and water is 9:1) of 0.4g polyvinylpyrrolidone (PVP) and 100mlDMSO, the mixed solution obtained stirs 15min; Then in mixed solution, logical nitrogen gets rid of oxygen 10min, then in mixed solution, add initiator A IBN0.1g, and control temperature reacts 6.0h at 50 DEG C, and then temperature rises to 70 DEG C of polymerization 18h.
4) the surface imprinted temperature-sensitivadsorbent adsorbent of product magnetic carbon nano-tube (TMMIPs) agent Nd-Fe-B permanent magnet is collected, 3 times are washed with absolute ethyl alcohol and distilled water, be finally extract 80 DEG C of soxhlet extractions with the mixed liquor that the volume ratio of methyl alcohol and acetic acid is 95:5, until can't detect 2 in eluent, 4,5-TCP, then vacuum drying at 50 DEG C.
5) in order to carry out comparative study, prepared the non-trace temperature-sensitivadsorbent adsorbent (TMNIPs) in magnetic carbon nano-tube surface in this work simultaneously, preparation method and the TMMIPs of TMNIPs are similar, the consumption of agents useful for same adds with reference to the consumption during TMMIPs that preparation is corresponding, just do not add 2,4,5-TCP.
2, absorption property test
(1) get 10ml initial concentration and be respectively 20mg/l, 50mg/l, 80mg/l, 100mg/l, 150mg/l, 2 of 200mg/l, 4, 5-TCP solution joins in plastic centrifuge tube, be 5.0 by watery hydrochloric acid or dilute sodium hydroxide adjust ph, add the surface imprinted temperature-sensitivadsorbent adsorbent TMMIPs of magnetic carbon nano-tube in 10mg the embodiment 1 and surface imprinted temperature-sensitivadsorbent adsorbent TMNIPs of magnetic carbon nano-tube respectively, test fluid is placed on after leaving standstill 12h in the water-bath of 25 DEG C, supernatant liquor Nd-Fe-B permanent magnet separated and collected, do not adsorb 2, 4, 5-TCP molecular concentration ultraviolet-uisible spectrophotometer measures (determined wavelength is 293nm), and calculate adsorption capacity according to result.Result shows, the saturated adsorption capacity of TMMIPs and TMNIPs 25 DEG C time is respectively 116.25mg/g and 95.76mg/g.
(2) after saturated adsorption, magnetic carbon nano-tube in embodiment 1 surface imprinted temperature-sensitivadsorbent adsorbent TMMIPs Nd-Fe-B permanent magnet is collected, add 10ml deionized water again, 12 hours are left standstill respectively in 30 DEG C and 40 DEG C of constant temperature waters, discharge 2,4,5-TCP content ultraviolet-uisible spectrophotometer measures, and calculates the release rate of template molecule according to result.Result shows, at 40 DEG C, 2,4,5-TCP of 81.54% absorption can be discharged by TMMIPs, and at 30 DEG C, 2,4,5-TCP of 66.69% absorption can be discharged by TMMIPs.Show that TMMIPs has good temperature control releasing effect.
(3) 2 are selected, 4-Dichlorophenol (DCP), sesamol (Sesamol), thymol (Thymol), the phenolic compound that bisphenol-A (BPA) is competitive Adsorption, be configured to the aqueous solution of four kinds of phenolic compounds respectively, the concentration of often kind of phenol is all 200mg/l, getting the solution that 10ml configures joins in plastic centrifuge tube, be 5.0 by watery hydrochloric acid or dilute sodium hydroxide adjust ph, add TMMIPs and the TMNIPs adsorbent in 10mg embodiment 1 respectively, test fluid is placed in the water-bath of 25 DEG C and leaves standstill 12h respectively, after time of repose completes, supernatant liquor Nd-Fe-B permanent magnet separated and collected, the various competitive Adsorption phenolic compound concentration ultraviolet-uisible spectrophotometers do not adsorbed measure, 2, 4, 5-TCP, Sesamol, Thymol, the determined wavelength of BPA and DCP is respectively 293nm, 293nm, 273nm, 276nm and 285nm.Result shows, TMMIPs is to 2,4, the adsorption capacity of 5-TCP, Sesamol, Thymol, BPA and DCP is respectively 180.32mg/g, 128.36mg/g, 96.12mg/g, 137.69mg/g and 108.59mg/g, and TMNIPs is to 2, the adsorption capacity of 4,5-TCP, Sesamol, Thymol, BPA and DCP is respectively 130.58mg/g, 103.58mg/g, 94.11mg/g, 117.54mg/g and 107.35mg/g.Show that TMMIPs has significant specific recognition ability to 2,4,5-TCP, adsorption capacity is higher than the phenolic compound of other competitive Adsorption.
3, material physicochemical property test
(1) transmission electron microscope (TEM) is utilized to test the pattern (see Fig. 1) of magnetic carbon nano-tube (MCNTs) and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube (TMMIPs) in embodiment 1.The Fe in MCNTs cavity can be found from figure
3o
4be about 20nm, trace polymer layer temperature sensitive in TMMIPs is about 25nm.
(2) Thermal Synthetic Analysis instrument is utilized to test the magnetic carbon nano-tube of magnetic carbon nano-tube, vinyl modified in embodiment 1 and the thermogravimetric curve figure (see Fig. 2) of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube.Can find from figure, the vinyl modified in the magnetic carbon nano-tube of vinyl modified accounts for 11% of weight, and in the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube, magnetic carbon nano-tube accounts for 11% of weight.
(3) measurement of vibration magnetic strength is utilized to try the hysteresis graph (see Fig. 3) of magnetic carbon nano-tube and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube in embodiment 1.Can find that from figure the saturated magnetic intensity of magnetic carbon nano-tube and the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube is respectively 3.4emu/g and 1.4emu/g, there is desirable Magnetic Isolation effect.
(4) absorbance figure (determined wavelength the is 542nm) (see figure 4) under utilizing ultraviolet specrophotometer to test the surface imprinted temperature-sensitivadsorbent adsorbent different temperatures of magnetic carbon nano-tube in embodiment 1.The minimum critical-temperature (LCST) of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube is about 36.2 as we know from the figure
oc.
Embodiment 2:
1, a preparation method for the surface imprinted temperature sensitive absorption of magnetic carbon nano-tube, is characterized in that carrying out according to following step:
(1) magnetic carbon nano-tube particle (MCNTs) is prepared
0.25g CNT and 0.2gFe (NO
3)
39H
2o to be dissolved in 12ml ethylene glycol and ultrasonic disperse 1.5h.Dispersion liquid heats 14h to obtain dry powder at 65 DEG C subsequently.Then, the dried powder of acquisition put into porcelain boat and proceeds to tube furnace, at propionic acid steam protection and 85 DEG C, heating 18h, powder continues at nitrogen protection and 280 DEG C, to heat 2.5h in tube furnace subsequently.Finally, the black product of cooling to proceed in beaker and with distilled water and absolute ethanol washing 3 times, washing afterproduct Nd-Fe-B permanent magnet reclaims, and is placed in vacuum drying chamber 60 DEG C of dry 8.0h, obtains magnetic carbon nano-tube particle.
(2) vinyl modified of magnetic carbon nano-tube particle:
Get 1.0g magnetic carbon nano-tube and be scattered in the dispersion liquid preparing magnetic carbon nano-tube in 180ml ethanol and water mixed liquid, and at room temperature stir 1.0h, wherein in ethanol and water mixed liquid, the volume ratio of second alcohol and water is (10:1).Subsequently, in the dispersion liquid of magnetic carbon nano-tube, add 5.0mlMPS, the mixed solution of acquisition stirs 24h at 45 DEG C.Then, the magnetic carbon nano-tube particle of vinyl modified Nd-Fe-B permanent magnet reclaims, and with distilled water and absolute ethanol washing 3 times.After washing, the magnetic carbon nano-tube particle of vinyl modified is placed in vacuum drying chamber 55 DEG C of dry 6.0h.
(3) preparation of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube:
1) by 1.0mmol2,4,5-TCP, 3.5mmol temperature sensitive monomer NIPAM, 1.4mmol function monomer AM dissolves in 15ml methyl-sulfoxide (DMSO).The mixed solution ultrasonic disperse 1.5h obtained, strengthens the pre-assembled of template molecule and function monomer, the pre-assembled solution of ultrasonic rear acquisition.
2) magnetic carbon nano-tube of 0.5g vinyl modified and 4.0ml oleic acid are placed in there-necked flask mechanical agitation 1.5h, mix the modified magnetic CNT that rear acquisition oleic acid infiltrates.Then in the modified magnetic CNT of oleic acid infiltration, add crosslinking agent EGDMA1.85ml, continue wherein subsequently to add above-mentioned pre-assembled solution, continue to stir 60min and obtain pre-polymer solution.
3) in above-mentioned pre-polymer solution, add the aqueous solution (in the aqueous solution of DMSO, the volume ratio of methyl-sulfoxide and water is 9:1) of 0.6g polyvinylpyrrolidone (PVP) and 120mlDMSO, the mixed solution obtained stirs 30min; Then in mixed solution, logical nitrogen gets rid of oxygen 15min, then in mixed solution, add initiator A IBN0.3g, and control temperature reacts 9.0h at 55 DEG C, and then temperature rises to 80 DEG C of polymerization 20h.
4) the surface imprinted temperature-sensitivadsorbent adsorbent of product magnetic carbon nano-tube (TMMIPs) agent Nd-Fe-B permanent magnet is collected, 3 times are washed with absolute ethyl alcohol and distilled water, be finally extract 80 DEG C of soxhlet extractions with the mixed liquor that the volume ratio of methyl alcohol and acetic acid is 95:5, until can't detect 2 in eluent, 4,5-TCP, then vacuum drying at 60 DEG C.
5) in order to carry out comparative study, prepared the non-trace temperature-sensitivadsorbent adsorbent (TMNIPs) in magnetic carbon nano-tube surface in this work simultaneously, preparation method and the TMMIPs of TMNIPs are similar, the consumption of agents useful for same adds with reference to the consumption during TMMIPs that preparation is corresponding, just do not add 2,4,5-TCP.
2, absorption property test
(1) get 10ml initial concentration and be respectively 20mg/l, 50mg/l, 80mg/l, 100mg/l, 150mg/l, 2 of 200mg/l, 4, 5-TCP solution joins in plastic centrifuge tube, be 5.0 by watery hydrochloric acid or dilute sodium hydroxide adjust ph, add the surface imprinted temperature-sensitivadsorbent adsorbent TMMIPs of magnetic carbon nano-tube in 10mg the embodiment 2 and surface imprinted temperature-sensitivadsorbent adsorbent TMNIPs of magnetic carbon nano-tube respectively, test fluid is placed on after leaving standstill 12h in the water-bath of 25 DEG C, supernatant liquor Nd-Fe-B permanent magnet separated and collected, do not adsorb 2, 4, 5-TCP molecular concentration ultraviolet-uisible spectrophotometer measures (determined wavelength is 293nm), and calculate adsorption capacity according to result.Result shows, the saturated adsorption capacity of TMMIPs and TMNIPs 25 DEG C time is respectively 121.32mg/g and 98.53mg/g.
(2) after saturated adsorption, magnetic carbon nano-tube in embodiment 2 surface imprinted temperature-sensitivadsorbent adsorbent TMMIPs Nd-Fe-B permanent magnet is collected, add 10ml deionized water again, 12 hours are left standstill respectively in 30 DEG C and 40 DEG C of constant temperature waters, discharge 2,4,5-TCP content ultraviolet-uisible spectrophotometer measures, and calculates the release rate of template molecule according to result.Result shows, at 40 DEG C, 2,4,5-TCP of 80.39% absorption can be discharged by TMMIPs, and at 30 DEG C, 2,4,5-TCP of 65.41% absorption can be discharged by TMMIPs.Show that TMMIPs has good temperature control releasing effect.
(3) 2 are selected, 4-Dichlorophenol (DCP), sesamol (Sesamol), thymol (Thymol), the phenolic compound that bisphenol-A (BPA) is competitive Adsorption, be configured to the aqueous solution of four kinds of phenolic compounds respectively, the concentration of often kind of phenol is all 200mg/l, getting the solution that 10ml configures joins in plastic centrifuge tube, be 5.0 by watery hydrochloric acid or dilute sodium hydroxide adjust ph, add TMMIPs and the TMNIPs adsorbent in 10mg embodiment 2 respectively, test fluid is placed in the water-bath of 25 DEG C and leaves standstill 12h respectively, after time of repose completes, supernatant liquor Nd-Fe-B permanent magnet separated and collected, the various competitive Adsorption phenolic compound concentration ultraviolet-uisible spectrophotometers do not adsorbed measure, 2, 4, 5-TCP, Sesamol, Thymol, the determined wavelength of BPA and DCP is respectively 293nm, 293nm, 273nm, 276nm and 285nm.Result shows, TMMIPs is to 2,4, the adsorption capacity of 5-TCP, Sesamol, Thymol, BPA and DCP is respectively 183.77mg/g, 124.32mg/g, 98.18mg/g, 132.55mg/g and 112.47mg/g, and TMNIPs is to 2, the adsorption capacity of 4,5-TCP, Sesamol, Thymol, BPA and DCP is respectively 134.82mg/g, 105.46mg/g, 97.25mg/g, 115.11mg/g and 109.68mg/g.Show that TMMIPs has significant specific recognition ability to 2,4,5-TCP, adsorption capacity is higher than the phenolic compound of other competitive Adsorption.
Claims (3)
1. a preparation method for the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube, carries out according to following step:
(1) magnetic carbon nano-tube particle is prepared:
By CNT, Fe (NO
3)
39H
2o and absolute ethyl alcohol are according to (0.22-0.25): (0.1-0.2): the ratio mixing also ultrasonic disperse 1.0-1.5h of (10-12) g/g/ml; Subsequently, above-mentioned dispersion liquid heats 12-14h to obtain dry powder at 60-65 DEG C; Then, the dried powder of acquisition put into porcelain boat and proceeds to tube furnace, at propionic acid steam protection and 80-85 DEG C, heating 15-18h, powder continues at nitrogen protection and 260-280 DEG C, to heat 2.0-2.5h in tube furnace subsequently; Finally, the black product of cooling to proceed in beaker and with distilled water and absolute ethanol washing 3 times, washing afterproduct Nd-Fe-B permanent magnet reclaims, and is placed in vacuum drying chamber 55-60 DEG C of dry 6.0-8.0h, obtains magnetic carbon nano-tube particle;
(2) vinyl modified of magnetic carbon nano-tube particle:
Prepare the dispersion liquid of magnetic carbon nano-tube particle according to every gram of magnetic carbon nano-tube particle dispersion in the ratio of 165-180ml ethanol and water mixed liquid, and at room temperature stir 0.5-1.0h; Subsequently, the ratio of 3.5-5.0ml3-(methacryloxypropyl) propyl trimethoxy silicane is added according to every gram of magnetic carbon nano-tube particle, in the dispersion liquid of above-mentioned magnetic carbon nano-tube particle, add 3-(methacryloxypropyl) propyl trimethoxy silicane, the mixed solution simultaneously obtained stirs 24h at 40-45 DEG C; Then, the magnetic carbon nano-tube particle of vinyl modified Nd-Fe-B permanent magnet reclaims, and with distilled water and absolute ethanol washing 3 times; After washing, the magnetic carbon nano-tube particle of vinyl modified is placed in vacuum drying chamber 50-55 DEG C of dry 5.0-6.0h;
(3) preparation of the surface imprinted temperature-sensitivadsorbent adsorbent of magnetic carbon nano-tube:
1) by 2,4,5-TCP, temperature sensitive monomer NIPAM, function monomer AM are 1.0:(3.5-4.0 in molar ratio): the ratio of (1.4-1.8) is dissolved in methyl-sulfoxide, and wherein the consumption of methyl-sulfoxide is every mM 2,4,5-TCP uses 10-15ml methyl-sulfoxide; The mixed solution ultrasonic disperse 1.0-1.5h obtained, strengthens the pre-assembled of template molecule and function monomer, the pre-assembled solution of ultrasonic rear acquisition;
2) magnetic carbon nano-tube of oleic acid and vinyl modified is placed in there-necked flask mechanical agitation 1.0-1.5h, the ratio of modified magnetic CNT and oleic acid is (0.25-0.5): (2.0-4.0) g/ml, obtains the modified magnetic CNT that oleic acid infiltrates after stirring; Then according to every mM 2,4,5-TCP adds the ratio of 1.46-1.85ml ethylene glycol bisthioglycolate (methacrylic acid) ester, crosslinking agent ethylene glycol bisthioglycolate (methacrylic acid) ester is added in the modified magnetic CNT that oleic acid infiltrates, continue the pre-assembled solution added in step 1) subsequently wherein, continue to stir 30-60min and obtain pre-polymer solution;
3) according to every mM 2,4,5-TCP adds the ratio of 0.4-0.6g polyvinylpyrrolidone and the 100-120ml methyl-sulfoxide aqueous solution, in step 2) in preparation pre-polymer solution in add the aqueous solution of polyvinylpyrrolidone and methyl-sulfoxide, the mixed solution obtained stirs 15-30min; Then in mixed solution, logical nitrogen gets rid of oxygen 10-15min, then in mixed solution according to every mM 2,4,5-TCP adds initator 2,2'-azodiisobutyronitrile 0.1-0.3g, and control temperature reacts 6.0-9.0h at 50-55 DEG C, then temperature obtains the surface imprinted temperature-sensitivadsorbent adsorbent of product magnetic carbon nano-tube after rising to 70-80 DEG C of polymerization 18-20h;
4) the surface imprinted temperature-sensitivadsorbent adsorbent Nd-Fe-B permanent magnet of product magnetic carbon nano-tube is collected, 3 times are washed with absolute ethyl alcohol and distilled water, be finally extract 80 DEG C of soxhlet extractions with the mixed liquor that the volume ratio of methyl alcohol and acetic acid is 95:5, until can't detect 2 in eluent, 4,5-TCP, then vacuum drying at 50-60 DEG C;
In ethanol wherein in step (2) and water mixed liquid, the volume ratio of second alcohol and water is (8-10): 1.
2. the preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube according to claim 1, it is characterized in that 2 of wherein step (3)) in add rapid 1 of step) in the amount of pre-assembled solution be: every mM 2,4,5-TCP need add the pre-assembled solution containing 10-15ml methyl-sulfoxide.
3. the preparation method of the surface imprinted temperature-sensitivadsorbent adsorbent of a kind of magnetic carbon nano-tube according to claim 1, is characterized in that 3 of wherein step (3)) in the methyl-sulfoxide aqueous solution volume ratio of methyl-sulfoxide and water be 9:1.
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