CN105749880A - Fulvic acid based magnetic ion imprinted polymer and preparation method thereof - Google Patents
Fulvic acid based magnetic ion imprinted polymer and preparation method thereof Download PDFInfo
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Abstract
Belonging to the technical field of ion imprinting, the invention provides a fulvic acid based magnetic ion imprinted polymer and a preparation method thereof. Specifically, the fulvic acid based magnetic ion imprinted polymer has a core-shell structure with Fe3O4/SiO2 composite magnetic particles as the magnetic core, and the magnetic core is coated with a functional shell. The functional shell is an ion imprinted polymer that adopts metal ion as the template and is obtained by crosslinking of a fulvic acid functional monomer. The product has the characteristics of stable structure, excellent selective recognition performance, fast adsorption of template ions, large adsorption capacity, reusability, and good magnetic separation effect. The preparation method comprises the steps of: 1) adopting a surface imprinting technique, taking fulvic acid as the functional monomer and metal ions as the template, under the action of a cross-linking agent, coating a Fe3O4/SiO2 composite magnetic particle surface with a fulvic acid crosslinked polymer; and 2) desorbing the metal ions to obtain the fulvic acid based magnetic ion imprinted polymer. The method has the advantages of simple process, low cost and small environmental pollution, and is convenient for intra-industry popularization and application.
Description
Technical field
The invention belongs to ionic imprinting technique field, be specifically related to yellow humic acidic group magnetic ion imprinted polymer and preparation method thereof.
Background technology
Ion imprinted polymer is a kind of novel high polymer material with Ion recognition character, and template ion has the ability quickly selecting and identifying.In recent years, ion imprinted polymer uses in fields such as Solid-Phase Extraction, chromatography, electrochemical sensor and pharmaceutical analysiss, especially surface ion imprinted polymer and application thereof, is the focus of research.
Nano ferriferrous oxide, except having bigger specific surface area, also has superparamagnetism, is prone to magnetization under additional the action of a magnetic field, and after externally-applied magnetic field disappears, remanent magnetism is zero.Adopt nanometer Fe3O4For core, high-molecular organic material is shell, and the surface ion imprinted polymer microsphere preparing nucleocapsid structure has the advantages such as sharp separation, good mechanical stability and saturated extent of adsorption are big.University of Fuzhou pays the ion imprinted polymer that phoenix richness etc. has methyl mercury ion physical structure three-dimensional hole in the synthesis of Fe 3 O 4 magnetic microsphere surface, it is achieved that to the preenrichment of special, the quick and high multiple of ultra trace methyl mercury in water body with separate (CN201510301721.0).Wuhan University Hu Bin etc. are with magnetic Fe3O4For core, outside core, wrap up SiO successively2Layer, mesoporous SiO2Layer and IIP layer prepare cadmium ion trace magnetic mesoporous silica gel solid phase extracting agent (CN201410586820.3).
Fulvic acid is a kind of environmental protection organic macromolecule material that humic acid middle-molecular-weihydroxyethyl is less, containing more carboxyl, hydroxyl and amino isoreactivity group in molecular structure, has good binding ability with metal ion.Research is had to confirm: fulvic acid is a kind of good adsorbent for heavy metal, and it is in the solution of partial neutral, to Cr6+、Fe3+、Cu2+The adsorbance of three metal ion species is relatively big, and adsorption effect stable (Zhou Shaoli, He Yan. the research [J] of chromium absorption behavior and mechanism on fulvic acid. coloured mining and metallurgy, 2007,23(6): 46-48；Zhou Shaoli, He Yan. the fulvic acid research [J] to ferrum absorption behavior. Shenyang Univ. of Science and Engineering journal .2007,26(6): 70-73；Zhou Shaoli, He Yan, Yang Yating. the research [J] of the fulvic acid absorption behavior to copper II and adsorption mechanism. application chemical industry .2010,39(2): 244-246).But directly fulvic acid is used as adsorbing material, there is ion packet buried depth, be difficult to the problems such as recycling, do not have commercial introduction and be worth.Considering that the imprinted polymer that traditional method polymerization prepares exists ion packet buried depth, eluting is difficult, prepare and reuse the drawback that cost is high, the present invention intends adopting fulvic acid to prepare magnetic ion imprinted polymer as function monomer.
Summary of the invention
The purpose of the present invention aims to provide a class yellow humic acidic group magnetic ion imprinted polymer, provides corresponding preparation method simultaneously.
For achieving the above object, this invention takes following technical scheme:
Yellow humic acidic group magnetic ion imprinted polymer, has with Fe3O4/SiO2Composite magnetic particle is the nucleocapsid structure that magnetic core, magnetic core are coated with function shell；Described function shell is to be template with metal ion, cross-linked by fulvic acid function monomer and the ion imprinted polymer that obtains.
Described metal ion is Ni2+。
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps: 1) adopt surface imprinted technology, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer；2) to step 1) products therefrom desorption metal ion, prepare yellow humic acidic group magnetic ion imprinted polymer and (be designated as Fe3O4/SiO2/ FA).
In described preparation method, cross-linking agent is KH-560；Described metal ion is Ni2+。
In described preparation method, the consumption proportion of each raw material is: fulvic acid 0.1～0.5g, metal ion 0.76～1.89mmol, cross-linking agent 0.2～5mL, Fe3O4/SiO2Composite magnetic particle 0.2～2g.
In described preparation method, the concrete operations of step 1) are: take fulvic acid solution and mix with bivalent soluble nickel salt solution, add cross-linking agent, are stirring evenly and then adding into Fe3O4/SiO2Composite magnetic particle, after ultrasonic vibration 5～30min at 50～70 DEG C mechanical agitation 12～36h.
In described preparation method, step 2) concrete operations be: step 1) products therefrom, after distilled water wash, is put into and is soaked desorption in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.1～0.5mol/L, dry.Described drying mode is preferred: dry at 35-55 DEG C.
Described Fe3O4/SiO2Composite magnetic particle prepares through following steps: a) adopt coprecipitation to prepare Fe3O4Nanoparticle；B) adopt sol-gal process at Fe3O4Nanoparticle surface parcel Si-O-Si structure.
The concrete operations of described step a) are: by FeSO4·7H2O and FeCl3·6H2O presses 1:(2.0～2.3) mol ratio in aqueous solvent with nitrogen for protective gas, constant temperature stirring and dissolving；It is warming up to 50～70 DEG C, quickly adds NH under stirring3·H2O；It is continuously heating to 80～95 DEG C, reacts 10～60min, namely obtain Fe with after the alternately washing of distilled water, dehydrated alcohol3O4Nanoparticle；The concrete operations of described step b) are: take 0.1～0.6g Fe prepared3O4Nanoparticle is scattered in 100mL volume ratio (0.1～10): in the ethanol/water mixed solvent of 1, adds 0.2～2mL ammonia and 0.5～10mL tetraethyl orthosilicate under mechanical stirring, stirs 2～10h under room temperature；Add excessive dissolving with hydrochloric acid and have neither part nor lot in the Fe of reaction3O4, then with the alternately washing of water, ethanol until neutral；Gained solid is dried, obtains Fe3O4/SiO2Composite magnetic particle.
A kind of yellow humic acidic group magnetic ion imprinted polymer, it is prepared by aforementioned preparation process.
Yellow humic acidic group magnetic ion imprinted polymer Stability Analysis of Structures provided by the invention, has excellent selection recognition performance, and template ion absorption is fast, and adsorption capacity is big, and in the research range of the present invention, maximal absorptive capacity is 2.11mg/g, and removal efficiency is 99.11%；Can repeatedly using, Magneto separate is respond well.
The preparation method advantage of the present invention is in that: use fulvic acid as the function monomer of preparation surface magnetism ion imprinted polymer, with Fe3O4/SiO2Being cross-linking agent for magnetic core, KH-560, combine with magnetic separation technique application by surface imprinted technology, and preparation process is simple, and with low cost, environmental pollution is little, it is simple to popularization and application in industry.
Accompanying drawing explanation
Fig. 1 is Fe in the present invention3O4、Fe3O4/SiO2And Fe3O4/SiO2The infrared spectrogram of/FA；
Fig. 2 is Fe in the present invention3O4、Fe3O4/SiO2And Fe3O4/SiO2The X-ray diffractogram of/FA；
Fig. 3 is FA and the Fe of embodiment 33O4/SiO2The thermogravimetric analysis figure of/FA；
Fig. 4 is the Fe of embodiment 53O4/SiO2/ FA is to Ni2+、Cr3+、Pb2+Competitive Adsorption curve；
Fig. 5 is the Fe of embodiment 53O4/SiO2/ FA in reusing process to Ni2+Adsorbance block diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.In embodiment, instrument includes: Fourier transform infrared spectrometer (Buddhist nun's high-tensile strength company of the U.S., AVATAR360 type)；X-ray diffractometer (Rigaku Co., Ltd., D/MAX2500PC)；Laser particle analyzer (Malvern company of Britain, Mastersizer2000)；Atomic Absorption Spectrometer (Beijing Puxi General Instrument Co., Ltd, TAS-986 type).
Embodiment 1
Fe is prepared by following steps3O4/SiO2Composite magnetic particle:
A) coprecipitation is adopted to prepare Fe3O4Nanoparticle: by FeSO4·7H2O and FeCl3·6H2O presses the mol ratio of 1:2.0 in aqueous solvent with nitrogen for protective gas, constant temperature stirring and dissolving；It is warming up to 60 DEG C, quickly adds NH under stirring3·H2O；It is continuously heating to 90 DEG C, reacts 30min, obtain Fe with separating after the alternately washing of distilled water, dehydrated alcohol3O4Nanoparticle (is designated as Fe3O4).
B) adopt sol-gal process at Fe3O4Nanoparticle surface parcel Si-O-Si structure: take the Fe that 0.4g step a) prepares3O4Nanoparticle, is scattered in 100mL ethanol/water mixed solvent (volume ratio is 4:1), adds 1mL ammonia and 1.5mL tetraethyl orthosilicate under mechanical stirring, stirs 6h under room temperature.Add excessive hydrochloric acid and dissolve the Fe having neither part nor lot in reaction3O4, then with the alternately washing of water, ethanol until neutral；Gained solid is dried, obtains Fe3O4/SiO2Composite magnetic particle (is designated as Fe3O4/SiO2).
Embodiment 2
Yellow humic acidic group magnetic ion imprinted polymer, with Fe3O4/SiO2Composite magnetic particle is the nucleocapsid structure that magnetic core, magnetic core are coated with function shell；Described function shell is to be template with metal ion, cross-linked by fulvic acid function monomer and the ion imprinted polymer that obtains.
Embodiment 3
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps:
1) surface imprinted technology is adopted, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent KH-560 effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer: taking the fulvic acid solution that 35mL concentration is 0.01g/mL is the NiCl of 0.03g/mL with 14mL concentration2·6H2O solution mixes, and adds 1.6mL cross-linking agent KH-560, is stirring evenly and then adding into the 0.6g Fe prepared3O4/SiO2Composite magnetic particle, after ultrasonic vibration 10min at 70 DEG C mechanical agitation 24h.
2) step 1) products therefrom is after distilled water wash, puts in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.25mol/L, soaks desorption metal ion Ni2+, until immersion can't detect Ni2+, dry at 45 DEG C, obtain yellow humic acidic group magnetic ion imprinted polymer and (be designated as Fe3O4/SiO2/ FA).
After testing, this product is to Ni2+Maximal absorptive capacity be 1.76mg/g, removal efficiency is 86.65%.
Embodiment 4
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps:
1) surface imprinted technology is adopted, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent KH-560 effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer: taking the fulvic acid solution that 30mL concentration is 0.01g/mL is the NiCl of 0.03g/mL with 12mL concentration2·6H2O solution mixes, and adds 1.2mL cross-linking agent KH-560, is stirring evenly and then adding into the 0.6g Fe prepared3O4/SiO2Composite magnetic particle, after ultrasonic vibration 10min at 60 DEG C mechanical agitation 24h.
2) step 1) products therefrom is after distilled water wash, puts in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.25mol/L, soaks desorption metal ion Ni2+, until immersion can't detect Ni2+, dry at 45 DEG C, obtain yellow humic acidic group magnetic ion imprinted polymer.
After testing, this product is to Ni2+Maximal absorptive capacity be 2.02mg/g, removal efficiency is 94.87%.
Embodiment 5
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps:
1) surface imprinted technology is adopted, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent KH-560 effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer: taking the fulvic acid solution that 30mL concentration is 0.01g/mL is the NiCl of 0.03g/mL with 12mL concentration2·6H2O solution mixes, and adds 1.2mL cross-linking agent KH-560, is stirring evenly and then adding into the 1g Fe prepared3O4/SiO2Composite magnetic particle, after ultrasonic vibration 10min at 60 DEG C mechanical agitation 36h.
2) step 1) products therefrom is after distilled water wash, puts in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.25mol/L, soaks desorption metal ion Ni2+, until immersion can't detect Ni2+, dry at 45 DEG C, obtain yellow humic acidic group magnetic ion imprinted polymer.
After testing, this product is to Ni2+Maximal absorptive capacity be 2.11mg/g, removal efficiency is 99.11%.
Embodiment 6
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps:
1) surface imprinted technology is adopted, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent KH-560 effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer: taking the fulvic acid solution that 10mL concentration is 0.01g/mL is the NiCl of 0.03g/mL with 6mL concentration2·6H2O solution mixes, and adds 0.2mL cross-linking agent KH-560, is stirring evenly and then adding into the 0.2g Fe prepared3O4/SiO2Composite magnetic particle, after ultrasonic vibration 5min at 60 DEG C mechanical agitation 30h.
2) step 1) products therefrom is after distilled water wash, puts in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.1mol/L, soaks desorption metal ion Ni2+, until immersion can't detect Ni2+, dry at 55 DEG C, obtain yellow humic acidic group magnetic ion imprinted polymer.
Embodiment 7
The preparation method of yellow humic acidic group magnetic ion imprinted polymer, comprises the following steps:
1) surface imprinted technology is adopted, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent KH-560 effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer: taking the fulvic acid solution that 50mL concentration is 0.01g/mL is the NiCl of 0.03g/mL with 15mL concentration2·6H2O solution mixes, and adds 5mL cross-linking agent KH-560, is stirring evenly and then adding into the 2g Fe prepared3O4/SiO2Composite magnetic particle, after ultrasonic vibration 30min at 50 DEG C mechanical agitation 12h.
2) step 1) products therefrom is after distilled water wash, puts in the disodiumedetate (EDETATE DISODIUM) that concentration is 0.5mol/L, soaks desorption metal ion Ni2+, until immersion can't detect Ni2+, dry at 35 DEG C, obtain yellow humic acidic group magnetic ion imprinted polymer.
Test 1 infrared spectrum analysis
The Fe of Example 1 preparation3O4、Fe3O4/SiO2And the product F e that embodiment 3 prepares3O4/SiO2/ FA carries out infrared spectrum analysis as laboratory sample, and gained collection of illustrative plates is as shown in Figure 1.It will be seen from figure 1 that at Fe3O4IR figure in, 3429cm-1The neighbouring bands of a spectrum occurred are to be caused by the stretching vibration peak of-OH, at 1621cm-1The neighbouring bending vibration that absworption peak is hydroxyl occurred causes.
At Fe3O4/SiO2IR figure in, 1642,1076,575cm-1Place is respectively belonging to the bending vibration peak of the bending vibration peak of H-O-H, the stretching vibration peak of Si-O-Si and Si-O, and this is all SiO2Infrared signature absorb.
At Fe3O4/SiO2The spectrogram of/FA finds, 3420cm-1-OH and the Fe that the characteristic peak that place occurs is probably in fulvic acid construction unit hydrogen bond and connects3O4/SiO2The stretching vibration feature of-OH overlap so that absworption peak area increases.It is primarily due to the absorption that the O-H stretching vibration of fulvic acid adds within the scope of this.By contrasting it is found that at Fe3O4/SiO2At 2935cm in/FA spectrogram-1There is a new peak in place, and this is the vibration peak of saturated aromatic hydrocarbons C-H.At 1612cm-1The peak at place belongs to the flexible vibrations peak of aromatic group C=C in molecule structure of fulvic acid, it was demonstrated that have the existence of aromatic core.Tentative confirmation fulvic acid is successfully immobilized on Fe3O4/SiO2Magnetic core surface.
Experiment 2X x ray diffraction analysis x
The Fe of Example 1 preparation3O4、Fe3O4/SiO2And the product F e that embodiment 3 prepares3O4/SiO2/ FA carries out X-ray diffraction analysis as laboratory sample, and result is as shown in Figure 2.In Fig. 2, the d value of diffraction maximum and standard magnetic Fe3O4The d value of characteristic diffraction peak be consistent with, illustrate that the microgranule that we prepare is Fe3O4Crystal.Figure has sharp-pointed diffraction maximum, particularly Fe3O4/SiO2The diffraction maximum of/FA, it was shown that obtained crystal structure is better, and particle size distribution is narrower.Fe3O4/SiO2The Fe of/FA and parcel silicon dioxide3O4The XRD figure of magnetic particle is composed all and Fe3O4Compare, 6 main diffraction peak of magnetic particle, as: (220), (311), (400), (422), (440), (511), its angle of diffraction is consistent with the Fe3O4 crystal of relative intensity Yu standard, illustrates that product is the Fe with cubic crystal structure3O4。Fe3O4/SiO2/ FA and Fe3O4/SiO2Paramagnetism is all without change, and the position of diffraction maximum is constant, and peak width is gradually increased, and this shows that great change does not occur crystal structure.The product F e that Example 4-7 prepares3O4/SiO2/ FA carries out X-ray diffraction analysis, and the result obtained is consistent with embodiment 3.
Test 3 thermogravimetric analysiss
With the product F e that embodiment 3 prepares3O4/SiO2/ FA is as testing sample, and contrast fulvic acid (FA) carries out thermogravimetric analysis, and result is as shown in Figure 3.From the figure 3, it may be seen that fulvic acid 80 DEG C begins to decompose, along with the rising of temperature, fulvic acid last decomposition, decomposition rate is basically unchanged.And imprinted polymer Fe3O4/SiO2The TG curve of/FA can be divided into three phases: room temperature ~ 250 DEG C, 250 DEG C ~ 550 DEG C, 550 DEG C ~ 850 DEG C.First stage (room temperature ~ 250 DEG C) declines to some extent, is because ion imprinted polymer and dries out；Second stage (250 DEG C ~ 550 DEG C) declines rapidly, and reason is wrapped around outermost fulvic acid and starts to decompose, mainly aliphatic series or fat ring scission, but due to fulvic acid and Fe3O4/SiO2There occurs that reaction, period have the generation of key, so adding the stability of fulvic acid.In this stage, ion imprinted polymer is weightlessness 15% about；The aromatic structure that phase III (550 DEG C ~ 850 DEG C) is relatively difficult decomposition in ion imprinted polymer is destroyed successively, Fe3O4/SiO2The Si-OH on surface dehydration gradually becomes Si-O-Si structure.In sum, the heat stability of ion imprinted polymer is significantly better than fulvic acid.
Test 4 adsorption effect tests
According to the Preliminary detection to product maximal absorptive capacity and removal efficiency, it is known that in the scope of present invention research, embodiment 5 is optimal case.Accordingly, Fe embodiment 5 prepared3O4/SiO2/ FA sample does the test of further competitive Adsorption: preparation Ni2+、Cu2+、Pb2+Concentration is the mixed solution of 5mg/L, pH value=6, is divided into three parts, every part of 50mL, adds 0.02gFe in every part of solution3O4/SiO2/ FA particle, after increase Fe successively3O4/SiO2The consumption of/FA, to 0.04g, 0.06g, 0.08g, 0.10g, 0.12g and 0.14g, carries out adsorption test, takes the meansigma methods of three groups of parallel tests, mapping, as shown in Figure 4.
As shown in Figure 4, increase along with ion imprinted polymer consumption, polymer is to Cr(III), Ni(II), Pb(II) clearance of three kinds of ions is all rising trend, wherein Ni(II) clearance rise very fast, when the consumption of ion imprinted polymer is 0.12g, now clearance is 99.35%, and after this, clearance is substantially constant；And Cr(III), Pb(II) two kinds of ion remaval rate ascensional ranges are less.Ion imprinted polymer is to Ni(II) adsorption effect significantly better than other two kinds of ions, to Cr(III) maximum material removal rate be 41.03%, to Pb(II) removal effect worst, maximum material removal rate is 20.14%, this illustrate ion imprinted polymer may identify which Ni(II).Simultaneously at Cr3+And Pb2+Under competing ions existent condition, have studied ion imprinted polymer to Ni2+、Cr3+And Pb2+Selection coefficient, its selectivity factor Ni2+/Cr3+、Ni2+/Pb2+It is 221.44 and 609.72 respectively.
Test 5 regeneration capacity tests
The quality of ion imprinted polymer performance is also embodied in reuses number of times.The ion imprinted polymer of embodiment 5 is carried out saturated adsorption capacity test, then with the EDTA of 0.25mol/L, ion imprinted polymer is carried out desorption process, 5 times so repeatedly, record each absorption-desorption periodic ion imprinted polymer to template ion Ni2+Saturated adsorption capacity, mapping, as shown in Figure 5.
Clearance measurements determination method: take 0.10g ion imprinted polymer and put in test bottle, adds 50mL and contains 5mg/LNi2+Solution, sampling filtering after separated in time, in analytical solution residual concentration of heavy metal ion, calculate the saturated adsorption capacity of ion imprinted polymer.
As can be seen from Figure 5, process through five absorption-desorptions, the saturated adsorption capacity of ion imprinted polymer is 2.10mg/g, 2.06mg/g, 2.01mg/g, 1.97mg/g and 1.92mg/g successively, through these five times, the saturated adsorption capacity of ion imprinted polymer reduces 0.18mg/g, change is little, it was shown that this ion imprinted polymer has good repeatability.
Claims (10)
1. yellow humic acidic group magnetic ion imprinted polymer, it is characterised in that have with Fe3O4/SiO2Composite magnetic particle is the nucleocapsid structure that magnetic core, magnetic core are coated with function shell；Described function shell is to be template with metal ion, cross-linked by fulvic acid function monomer and the ion imprinted polymer that obtains.
2. yellow humic acidic group magnetic ion imprinted polymer as claimed in claim 1, it is characterised in that described metal ion is Ni2 +。
3. the preparation method of yellow humic acidic group magnetic ion imprinted polymer, it is characterised in that comprise the following steps: 1) adopt surface imprinted technology, with fulvic acid for function monomer, with metal ion for template, under cross-linking agent effect, at Fe3O4/SiO2Composite magnetic particle Surface coating fulvic acid cross linked polymer；2) to step 1) products therefrom desorption metal ion, yellow humic acidic group magnetic ion imprinted polymer is prepared.
4. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as claimed in claim 3, it is characterised in that described cross-linking agent is KH-560；Described metal ion is Ni2+。
5. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as claimed in claim 4, it is characterised in that the consumption proportion of each raw material is: fulvic acid 0.1～0.5g, metal ion 0.76～1.89mmol, cross-linking agent 0.2～5mL, Fe3O4/SiO2Composite magnetic particle 0.2～2g.
6. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as described in claim 4 or 5, it is characterised in that the concrete operations of described step 1) are: take fulvic acid solution and mix with bivalent soluble nickel salt solution, adds cross-linking agent, is stirring evenly and then adding into Fe3O4/SiO2Composite magnetic particle, after ultrasonic vibration 5～30min at 50～70 DEG C mechanical agitation 12～36h.
7. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as claimed in claim 6, it is characterized in that, described step 2) concrete operations be: step 1) products therefrom, after distilled water wash, puts in the disodiumedetate that concentration is 0.1～0.5mol/L immersion desorption, dry.
8. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as described in claim 3 or 7, it is characterised in that described Fe3O4/SiO2Composite magnetic particle prepares through following steps: a) adopt coprecipitation to prepare Fe3O4Nanoparticle；B) adopt sol-gal process at Fe3O4Nanoparticle surface parcel Si-O-Si structure.
9. the preparation method of yellow humic acidic group magnetic ion imprinted polymer as claimed in claim 8, it is characterised in that the concrete operations of described step a) are: by FeSO4·7H2O and FeCl3·6H2O presses 1:(2.0～2.3) mol ratio in aqueous solvent with nitrogen for protective gas, constant temperature stirring and dissolving；It is warming up to 50～70 DEG C, quickly adds NH under stirring3·H2O；It is continuously heating to 80～95 DEG C, reacts 10～60min, namely obtain Fe with after the alternately washing of distilled water, dehydrated alcohol3O4Nanoparticle；The concrete operations of step b) are: take 0.1～0.6g Fe prepared3O4Nanoparticle is scattered in 100mL volume ratio (0.1～10): in the ethanol/water mixed solvent of 1, adds 0.2～2mL ammonia and 0.5～10mL tetraethyl orthosilicate under mechanical stirring, stirs 2～10h under room temperature；Add excessive dissolving with hydrochloric acid and have neither part nor lot in the Fe of reaction3O4, then with the alternately washing of water, ethanol until neutral；Gained solid is dried, obtains Fe3O4/SiO2Composite magnetic particle.
10. a yellow humic acidic group magnetic ion imprinted polymer, it is prepared by the arbitrary described preparation method of claim 3-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750316A (en) * | 2017-01-16 | 2017-05-31 | 南华大学 | A kind of preparation method of magnetic core-shell nanoparticle surface uranyl molecularly imprinted polymer |
| CN110394164A (en) * | 2019-07-29 | 2019-11-01 | 肇庆学院 | A kind of heavy metal ion magnetic imprinted polymer and preparation method thereof |
| CN115090275A (en) * | 2022-06-10 | 2022-09-23 | 南京工业大学 | Nano composite material for sewage treatment and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303046B1 (en) * | 1997-08-08 | 2001-10-16 | William M. Risen, Jr. | Aerogel materials and detectors, liquid and gas absorbing objects, and optical devices comprising same |
| CN102527349A (en) * | 2011-11-28 | 2012-07-04 | 江苏大学 | Magnetic composite material surface imprinting thermosensitive adsorbent, and preparation method and application thereof |
-
2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303046B1 (en) * | 1997-08-08 | 2001-10-16 | William M. Risen, Jr. | Aerogel materials and detectors, liquid and gas absorbing objects, and optical devices comprising same |
| CN102527349A (en) * | 2011-11-28 | 2012-07-04 | 江苏大学 | Magnetic composite material surface imprinting thermosensitive adsorbent, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘静欣等: "交联腐殖酸CHA对水体中铅的吸附性能", 《环境工程学报》 * |
| 张小梅: "磁性离子印迹聚合物的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750316A (en) * | 2017-01-16 | 2017-05-31 | 南华大学 | A kind of preparation method of magnetic core-shell nanoparticle surface uranyl molecularly imprinted polymer |
| CN110394164A (en) * | 2019-07-29 | 2019-11-01 | 肇庆学院 | A kind of heavy metal ion magnetic imprinted polymer and preparation method thereof |
| CN110394164B (en) * | 2019-07-29 | 2021-09-17 | 肇庆学院 | Heavy metal ion magnetic imprinted polymer and preparation method thereof |
| CN115090275A (en) * | 2022-06-10 | 2022-09-23 | 南京工业大学 | Nano composite material for sewage treatment and application thereof |
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