CN110394164B - Heavy metal ion magnetic imprinted polymer and preparation method thereof - Google Patents
Heavy metal ion magnetic imprinted polymer and preparation method thereof Download PDFInfo
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- CN110394164B CN110394164B CN201910690970.1A CN201910690970A CN110394164B CN 110394164 B CN110394164 B CN 110394164B CN 201910690970 A CN201910690970 A CN 201910690970A CN 110394164 B CN110394164 B CN 110394164B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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Abstract
The invention provides a magnetic imprinted polymer and a preparation method thereof, wherein the magnetic imprinted polymer with specific recognition and selective adsorption on target heavy metal ions is obtained by silicification of yeast, formation of a core-shell type polymeric structure with magnetic nanoparticles in a target heavy metal ion solution by utilizing rich multifunctional bond components on the surface of the yeast, and elution of the target heavy metal ions. The method takes the silicified saccharomycetes as the functional monomer, not only realizes the comprehensive utilization of the saccharomycetes, but also improves the safety of the magnetic imprinted polymer, has the characteristics of excellent economy, large adsorption capacity, high selectivity, good stability, long service life, simple preparation process and the like, and has wide application prospect in the rapid magnetic separation, enrichment and analysis of heavy metal ions in environmental samples, biological samples, agricultural products and food.
Description
Technical Field
The invention relates to the field of heavy metal ion enrichment, and particularly relates to a heavy metal ion magnetic imprinted polymer and a preparation method thereof.
Background
With the development of modern industry, the development mode of environmental protection is more and more emphasized by people. The problem of the hazard caused by heavy metals is well known to the public and numerous treatments, including physical, chemical; at present, the harmless and recycling treatment technology of heavy metal wastewater mainly comprises chemical conversion technology such as an electrolytic method and the like; media extraction techniques such as solvent extraction, ion exchange, adsorption, and the like; physical chemical concentration techniques such as electrodialysis, membrane permeation, etc. The ion concentration in the actual heavy metal polluted wastewater is generally lower, and if the traditional treatment method is adopted, the efficiency is low, the cost is high, and the operation is complicated.
The magnetic molecular imprinting technology not only has stronger adsorption capacity to heavy metals, but also has the characteristic of controllable magnetic separation, avoids complex concentration and classification processes such as centrifugation, filtration and the likeThe application of the heavy metal field is widely concerned, and Chinese patent CN103709342B discloses a preparation method of a magnetic cadmium ion surface imprinted polymer, which uses Fe3O4@SiO2Preparing a magnetic surface imprinted polymer by using microspheres as a carrier, Cd (II) as a template, ethylene glycol dimethacrylate as a cross-linking agent and methacrylic acid and salicylaldoxime as monomers; chinese patent CN105884985A discloses a magnetic cadmium ion imprinted polymer and a preparation method thereof, namely Fe modified by vinyl3O4@SiO2Being a magnetic carrier, Cd2+Any two of methacrylic acid, acrylamide and vinyl pyridine are taken as functional monomers as a template, ethylene glycol dimethacrylate is taken as a cross-linking agent, and azodiisobutyronitrile is taken as an initiator.
The existing magnetic imprinted polymer has the defects of small adsorption capacity and low reuse rate, and on the other hand, the existing magnetic imprinted polymer generally takes methacrylic acid, salicylaldoxime, acrylamide, vinylpyridine and the like as functional monomers, and the chemical compounds have certain toxicity to human bodies and certain risks in detection of food samples.
Disclosure of Invention
Aiming at the problems, the invention provides a heavy metal ion magnetic imprinted polymer and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a heavy metal ion magnetic imprinted polymer comprises the following steps:
(1) preparation of Fe3O4@SiO2；
(2) Adding the suspension of the yeast into TEOS and HCl solution, heating in water bath, stirring, reacting, and filtering to obtain silicified yeast;
(3)Fe3O4@SiO2adding methanol, rapidly stirring to obtain solution A, adding methanol mixed water bath into the solution of target heavy metal ion, heating, adding silicified yeast, stirring and refluxing, adding solution A, stirring and refluxing, magnetically separating to obtain product, eluting target heavy metal ion, and vacuum drying to obtain the heavy metal ion magneticA sexually imprinted polymer;
preferably, the mixing ratio of the yeast and distilled water in the suspension of the yeast in the step (2) is 30-70mL/g, the concentration of HCl solution is 2mol/L, and the adding amount of TEOS, HCl solution and yeast is 1 mL/g;
preferably, the water bath heating and stirring reaction conditions in the step (2) are that the temperature is 20-50 ℃, the stirring speed is 200-700rpm, and the stirring time is 30-120 min;
preferably, Fe in the solution A in the step (3)3O4@SiO2The mixing ratio of the methanol and the water bath is 30-70mL/g, and the heating temperature of the water bath is 50-90 ℃;
preferably, the yeast silicide and TEOS and Fe in step (3)3O4@SiO2The adding mass ratio of (1-5) g/g, and the stirring reflux time is 12-36 h;
preferably, the elution in the step (3) is that deionized water and ethanol are respectively used for washing, EDTA solution is used for washing under the ultrasonic condition until the washing solution can not detect the target heavy metal ions, and then methanol is used for washing;
further preferably, the concentration of the EDTA solution is 0.05-0.5 mol.L-1；
Preferably, the vacuum drying temperature in the step (3) is 40-80 ℃;
preferably, the yeast is saccharomyces cerevisiae, and further preferably is saccharomyces cerevisiae;
preferably, the target heavy metal ion is Cd2+、Co2+、Ni2+、Cu2+、Zn2+、Hg2+、Pb2+、Sn2+One kind of (1).
The second purpose of the present application is to provide a heavy metal magnetic imprinted polymer, which is prepared by any one of the above preparation methods.
The application also aims to provide an application of the heavy metal magnetic imprinted polymer, wherein the application comprises detection, enrichment and/or separation of corresponding heavy metals in a sample to be detected.
The invention has the beneficial effects that:
aiming at the defects of the prior art, the modified saccharomycete is used as a functional monomer, a target heavy metal ion is used as a template, and a surface imprinting method is used for preparing the magnetic imprinting polymer.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a schematic diagram of a preparation process of the heavy metal magnetic imprinted polymer;
FIG. 2 is a graph of the relationship between the number of times of repeated use and the recovery rate of the heavy metal magnetic imprinted polymer.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of a cadmium ion magnetic imprinted polymer comprises the following steps:
(1) containing 11.2mmol of Fe3+And 5.6mmol Fe2+Introducing nitrogen into 150mL of the aqueous solution to remove oxygen, heating to 80 ℃, stirring at 500rmp, and introducing N2Under these conditions, 12.5mL of 25 wt.% NH was added rapidly3·H2O, reacting in a constant-temperature water bath at 80 ℃ for 30min, standing, magnetically attracting magnetic nanoparticles by a magnet, pouring out supernatant, washing for 4 times by absolute ethyl alcohol and deoxygenated water (secondary double distilled water) until the pH value is about 7 to remove impurities, and drying in vacuum;
480mL of water is added with 3.5mL of 2mol/L NaOH, stirred in a water bath at 80 ℃ at 350rpm for 15min, and added with the Fe obtained by the preparation3O4160mg of magnetic nano particles, continuously stirring for 15min, dropwise adding 2ml TEOS (after 5 min), and reacting to obtain TEOS and water substances in the reaction systemThe amount ratio of the raw materials is 1:70, the reaction time is 2 hours, the ethanol is washed for 3 to 4 times after the reaction is finished, and the raw materials are dried for 1 hour at 120 ℃;
(2) adding 5.0g of saccharomyces cerevisiae into a three-neck flask, adding 150mL of distilled water for soaking to obtain a saccharomyces cerevisiae suspension, adding 5mL of TEOS and 5mL of 2mol/L HCl solution, heating in a water bath at 35 ℃, stirring for reaction for 1h, and filtering to obtain silicified saccharomyces cerevisiae;
(3)1.0g Fe3O4@SiO2adding 50mL of methanol and rapidly stirring to obtain a solution A and 1.0mmol of Cd (NO)3)2Dissolving in 30mL water, adding methanol with twice volume, heating in 70 deg.C water bath, adding silicified cerevisiae Fermentum 3.0g and TEOS 3.0g, stirring and refluxing, adding solution A, stirring and refluxing for 24 hr, magnetically separating to obtain product, washing with deionized water and ethanol, and repeatedly using 0.1 mol/L under ultrasonic action-1EDTA Wash until no Cd could be detected2+And then washing the mixture for 3 times by using methanol, and drying the mixture in a vacuum drier at the temperature of 50 ℃ for 6 hours to prepare the cadmium ion magnetic imprinted polymer.
Examples 2 to 7
Cd (NO) based on example 13)2Are respectively replaced by Co2+、Ni2+、Cu2+、Zn2+、Hg2+、Pb2+、Sn2+Respectively preparing the magnetic imprinted polymer which specifically adsorbs corresponding metal ions.
Example 8
The cadmium ion magnetic imprinted polymer prepared in example 1 is used for establishing a magnetic solid phase extraction-graphite furnace atomic absorption spectrometry method, and is applied to Cd in environment and food samples2+The determination of (1): adding 0.03g of the cadmium ion magnetic imprinted polymer prepared in example 1 into 100mL of the treated sample solution, adjusting the pH value of the solution to 6 by using hydrochloric acid and sodium hydroxide, carrying out ultrasonic treatment and activation at normal temperature, oscillating for 10min, carrying out magnetic separation, washing twice by using 10.0mL of deionized water, carrying out magnetic separation, and washing twice by using 10.0mL of 0.5 mol.L-1Performing ultrasonic washing with EDTA for 10min, blowing nitrogen gas into the obtained solution, evaporating to dryness, diluting to 50mL with 0.1% nitric acid, and analyzing Cd by graphite furnace atomic absorption spectrometry2+The results are shown in Table 1.
TABLE 1 measurement of cadmium in different water samples and beer (n ═ 3)
Cd in sample2+The measured recovery rate ranges from 86.4% to 99.1%, and the relative standard deviation is less than 4.7%, indicating that the result is accurate and reliable. Cd is detected in the detected samples2+The measured values in the water samples and beer were at normal levels.
Examples of the experiments
The influence of the repeated use times on the recovery rate is measured, and the measurement result is shown in fig. 2, the recovery rate is 90.7% after the cadmium ion magnetic imprinted polymer is repeatedly used for 4 times, the recovery rate is 81.0% after the cadmium ion magnetic imprinted polymer is repeatedly used for 8 times, and the recovery rate is 73.6% after the cadmium ion magnetic imprinted polymer is repeatedly used for 10 times, which indicates that the cadmium ion magnetic imprinted polymer has good stability and long service life.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the heavy metal ion magnetic imprinted polymer is characterized by comprising the following steps:
(1) preparation of Fe3O4@SiO2；
(2) Adding the suspension of the yeast into TEOS and HCl solution, heating in water bath, stirring, reacting, and filtering to obtain silicified yeast;
（3）Fe3O4@SiO2adding methanol, stirring rapidly to obtain solution A, adding the solution of target heavy metal ions into methanol mixed water bath, heating, adding silicified yeast and TEOS, stirring and refluxing, adding solution A, stirring and refluxing, magnetically separating to obtain product, mixingEluting target heavy metal ions, and drying in vacuum to obtain the heavy metal ion magnetic imprinted polymer.
2. The method for preparing a heavy metal ion magnetic imprinted polymer according to claim 1, wherein the mixing ratio of the yeast to the distilled water in the yeast suspension of the step (2) is 30-70mL/g, and the concentration of the HCl solution is 2 mol-L-1The adding proportion of TEOS, HCl solution and yeast is 1 mL/g.
3. The method for preparing a heavy metal ion magnetic imprinted polymer as claimed in claim 1, wherein the water bath heating stirring reaction conditions in step (2) are temperature of 20-50 ℃, stirring speed of 200-700rpm, and stirring time of 30-120 min.
4. The method for preparing the heavy metal ion magnetic imprinted polymer according to claim 1, wherein the Fe in the solution A in the step (3) is Fe3O4@SiO2The mixing ratio of the methanol and the water bath is 30-70mL/g, and the heating temperature of the water bath is 50-90 ℃.
5. The method for preparing a heavy metal ion magnetic imprinted polymer according to claim 1, wherein the step (3) comprises silicification of yeast and TEOS and Fe3O4@SiO2The addition mass ratio of (A) is 1-5g/g, and the stirring reflux time is 12-36 h.
6. The method for preparing a heavy metal ion magnetic imprinted polymer according to claim 1, wherein the elution in the step (3) is performed by washing with deionized water and ethanol respectively, and performing ultrasonic treatment at a concentration of 0.05-0.5 mol.L-1 Washing with EDTA solution until the washing solution can not detect the target heavy metal ions, and washing with methanol.
7. The method for preparing the heavy metal ion magnetic imprinted polymer according to claim 1, wherein the yeast is saccharomyces cerevisiae.
8. The preparation method of the heavy metal ion magnetic imprinted polymer according to claim 1, wherein the target heavy metal ion is Cd2+、Co2+、Ni2+、Cu2+、Zn2+、Hg2+、Pb2+、Sn2+One kind of (1).
9. The heavy metal magnetic imprinted polymer prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the heavy metal magnetic imprinted polymer according to claim 9 for detection, enrichment and/or separation of the corresponding heavy metal in a sample to be tested.
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| WO2003086612A1 (en) * | 2002-04-10 | 2003-10-23 | Ufc Limited | Method of producing dynamic combinatorial libraries |
| CN103657608A (en) * | 2013-12-02 | 2014-03-26 | 江苏大学 | Preparation method and application of magnetic silicon-coated yeast grafted polyethyleneimine biological composite material |
| CN104086688A (en) * | 2014-07-03 | 2014-10-08 | 江苏大学 | Method for preparing core-shell yeast/styrene molecularly-imprinted polymers through miniemulsion polymerization |
| CN105749880A (en) * | 2016-03-07 | 2016-07-13 | 华北理工大学 | Fulvic acid based magnetic ion imprinted polymer and preparation method thereof |
| EP3112021A1 (en) * | 2015-06-29 | 2017-01-04 | Centre National de la Recherche Scientifique (C.N.R.S.) | Preparation of molecularly imprinted polymers by two-photon stereolithography |
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| JP5968532B2 (en) * | 2012-07-06 | 2016-08-10 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Method for producing a polymer adhesive composition comprising inorganic particles |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086612A1 (en) * | 2002-04-10 | 2003-10-23 | Ufc Limited | Method of producing dynamic combinatorial libraries |
| CN103657608A (en) * | 2013-12-02 | 2014-03-26 | 江苏大学 | Preparation method and application of magnetic silicon-coated yeast grafted polyethyleneimine biological composite material |
| CN104086688A (en) * | 2014-07-03 | 2014-10-08 | 江苏大学 | Method for preparing core-shell yeast/styrene molecularly-imprinted polymers through miniemulsion polymerization |
| EP3112021A1 (en) * | 2015-06-29 | 2017-01-04 | Centre National de la Recherche Scientifique (C.N.R.S.) | Preparation of molecularly imprinted polymers by two-photon stereolithography |
| CN105749880A (en) * | 2016-03-07 | 2016-07-13 | 华北理工大学 | Fulvic acid based magnetic ion imprinted polymer and preparation method thereof |
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