CN103254354A - Cadmium ion imprinted adsorbent, and preparation method and application thereof - Google Patents
Cadmium ion imprinted adsorbent, and preparation method and application thereof Download PDFInfo
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- CN103254354A CN103254354A CN2013102005274A CN201310200527A CN103254354A CN 103254354 A CN103254354 A CN 103254354A CN 2013102005274 A CN2013102005274 A CN 2013102005274A CN 201310200527 A CN201310200527 A CN 201310200527A CN 103254354 A CN103254354 A CN 103254354A
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Abstract
The invention discloses a cadmium ion imprinted adsorbent, and a preparation method and application thereof, belonging to the technical field of preparation adsorbing materials. The preparation method comprises the following steps: (1) forming a chelate from cadmium ions and functional monomers; (2) crosslinking the chelate into a polymer under the action of a crosslinking agent; and (3) washing the polymer with an eluate to remove the cadmium ions to form the cadmium ion imprinted adsorbent. The cadmium ion imprinted adsorbent disclosed by the invention is prepared by a mass polymerization method, and synthesizes a solid-phase extraction material by using methacrylic acid and 4-vinyl pyridine as the functional monomers and ethylene glycol dimethyl acrylate as the crosslinking agent; and the solid-phase extraction material has the advantages of high bonding firmness, stable properties, favorable reproducibility and high selectivity. The adsorbent can be used in enrichment pretreatment of trace amounts of Cd (II) in an ambient water sample.
Description
Technical field
The invention belongs to sorbing material preparation technology field, be specifically related to a kind of cadmium ion trace sorbent material and its preparation method and application.
Background technology
Cadmium is to produce alloy, battery, and the important meals element of dyestuff and plated material etc., however contain in the industrial waste waste water inflow environment of cadmium, will cause the deterioration of environment.Because heavy metal cadmium is difficult for by biological degradation, cadmium can enter human body by food chain and respiratory tract, and the sedimentation accumulation produces serious harm to HUMAN HEALTH, so particularly important to the monitoring of cadmium metal in human body.In recent years, the method that detects for the environmental water sample heavy metal content mainly contains flame atomic absorption spectrophotometer (FAAS), sampling Graphite Furnace Atomic Absorption spectrophotometer (GFAAS) and inductively coupled plasma emission spectrography (ICP-AES) etc.Wherein FAAS because have low consumption, advantage such as easy and simple to handle is widely used.Yet, since in the environmental water sample in the content of heavy metal extremely low (as underground water national standard one class water quality Cd (II) less than 0.0001mg/L) and the water sample other metal pair detected result have very big interference, therefore, need carry out separation and concentration to environmental water sample handles.In numerous separation methods, solid phase extraction techniques (SPE) is owing to have that rate of recovery height, organic solvent consumption less, effectively separate and easy to operate and advantage such as easily be automated and show one's talent.At present, SPE has been widely used in fields such as food safety, environment, medical treatment, pharmaceutical analysis, chemical industry.And the development high-performance, high absorption, the sorbing material of high enrichment multiple is the key of solid phase extraction techniques, is subjected to investigator's great attention.
Molecular imprinting refers to prepare the polymkeric substance that a certain specific target molecules is had specific selectivity.It is that the target molecule that will separate is as template molecule, polymerization is carried out in it and linking agent in polymer monomer solution, prepare monomer-template molecule mixture, remove template molecule by physics or chemical process then, just obtain having the molecularly imprinted polymer of target molecule space structure.This polymer formation have similar space and the hole of binding site to template molecule, such hole has more selectivity to template molecule.The template of ion imprinted polymer is metal ion, and is similar to molecularly imprinted polymer, has all advantages of molecularly imprinted polymer, is widely used in separation and the detection of metal ion in recent years.Taher Alizadeh (Journal of Electroanalytical Chemistry, 2011,657:98-106) etc. employing vinyl pyridine and quinardinic acid are function monomer, have prepared the cadmium ion imprinted polymer.Yongwen Liu (Analytica Chimica Acta, 2004,519:173-179) etc. employing vinyl pyridine and diazo aminobenzene are that function monomer, ethylene glycol dimethacrylate are linking agent, have synthesized the cadmium ion imprinted polymer, are used for the separation and concentration of cadmium.At present, not seeing as yet and adopting 4-vinylpridine and methacrylic acid is that function monomer, ethylene glycol dimethacrylate are linking agent, the relevant report of synthetic cadmium ion trace sorbent material.
Summary of the invention
The object of the present invention is to provide a kind of cadmium ion trace sorbent material and its preparation method and application, cadmium ion trace Solid-Phase Extraction material provided by the present invention adopts molecular imprinting, and bonding is firm, stable in properties, favorable reproducibility, and selectivity is good.This sorbent material can be used for the enrichment pre-treatment of trace Cd in the environmental water sample (II).
For achieving the above object, the present invention adopts following technical scheme:
A kind of cadmium ion trace preparation of adsorbent method may further comprise the steps:
(1) with 1 mmol CdCl
2Be dissolved in 15 ~ 20 mL dimethyl sulfoxide (DMSO) with 2 ~ 4 mmol function monomers, solution at room temperature magnetic agitation 1 h forms the cadmium ion inner complex; Described function monomer is methacrylic acid and 4-vinylpridine, and both mol ratios are 1:1;
(2) 0.1 ~ 0.2 g Diisopropyl azodicarboxylate and 20 mmol ethylene glycol dimethacrylates are dissolved in 2 ~ 3 mL dimethyl sulfoxide (DMSO), under nitrogen protection, mix with solution in the step (1), 70 ℃ of water-bath 24 h form polymkeric substance;
(3) polymkeric substance that forms in the step (2) is used earlier washing with alcohol, removes the template cadmium ion with the washing of 2 mol/L hydrochloric acid solns subsequently, is washed till neutrality with secondary deionized water at last, the loft drier drying.
Described this sorbent material is used for the enrichment pre-treatment of environmental water sample trace Cd (II).
Remarkable advantage of the present invention is:
(1) the cadmium ion trace sorbent material that synthesizes of the present invention is to be function monomer with 4-vinylpridine and methacrylic acid, and ethylene glycol dimethacrylate is that linking agent is polymerized, and has good stability.
(2) the cadmium ion trace sorbent material that synthesizes of the present invention adopts molecular imprinting, can improve the selectivity to cadmium.
(3) the cadmium ion trace sorbent material that synthesizes of the present invention has favorable reproducibility, can reuse the advantage that reproducibility is good.
Description of drawings
Fig. 1 is the cadmium ion trace of pH adsorbents adsorb Cd (II) Effect on Performance.
Embodiment
Embodiment 1
Cadmium ion trace preparation of adsorbent
(1) with 1 mmol CdCl
2, 2 ~ 4 mmol methacrylic acids, 4-vinylpridine function monomer are dissolved in the dimethyl sulphoxide solution of 15 ~ 20 mL, and solution at room temperature magnetic agitation 1 h forms the cadmium ion inner complex;
(2) 0.1 ~ 0.2 g Diisopropyl azodicarboxylate and 20 mmol ethylene glycol dimethacrylates are dissolved in the dimethyl sulphoxide solution of 2 ~ 3 mL.Under nitrogen protection, mix 70 ℃ of water-bath 24 h with solution in the step (1);
(3) polymkeric substance that forms in the step (2) is used earlier washing with alcohol, and with 2 M hydrochloric acid solns washing flush away template cadmium ion, last secondary deionized water is washed till neutrality, the loft drier drying for standby subsequently;
Embodiment 2
The cadmium ion trace of pH adsorbents adsorb Effect on Performance
By the static test to different pH value, adopt flame atomic absorption method (FAAS) to record its specific absorption.Fig. 1 is the cadmium ion trace of pH adsorbents adsorb Cd (II) Effect on Performance, the ionic concn of its initial Cd (II): 1.0 mg/L; Sorbent material consumption: 0.3g; Duration of oscillation: 30 min; Temperature: 25 ℃; Volume of sample: 100 mL.
Embodiment 3
Maximum enrichment multiple is measured
By the dynamic experiment method, to have investigated under the various sample volume conditions, cadmium ion trace sorbent material is to the enrichment performance of Cu (II).Experiment will contain 200,400,600 of 10 μ g Cd (II) respectively, 800, the sample solution of 1000,1200 and 1400 mL descended the column extracting enrichment in the best extraction and elution requirement, then by the mensuration of Cd (II) rate of recovery is studied its maximum enrichment multiple.The result is as shown in table 1, and when volume of sample increased to 1400 mL, the rate of recovery of Cd (II) was down to 84.5 %.This explanation cadmium ion trace sorbent material has good extracting and enriching ability to Cd (II), because 8 mL hydrochloric acid solns just can be realized quantitative recovery Cd (II), so its maximum enrichment multiple is 150, be expected to realization to the extracting and enriching of ppb level Cd (II) in the sample solution.
Table 1 is that cadmium ion trace sorbent material is to the maximum volume of sample of Cd (II) and enrichment multiple
Embodiment 4
The reproducibility of sorbent material
Get 0.15 g cadmium ion trace sorbent material as the SPE column material, 10 mL, 1 mg/L Cd (II) solution was descended the SPE post at optimum extraction condition, remain in the Cd (II) that is not adsorbed on sorbent material and the SPE post with the secondary deionized water flush away then, wash-out Cd (II) under the optimum washing engaging condition of having optimized, FAAS measures the Cd (II) in the elutriant.Cross post with certain density hydrochloric acid afterwards, to remove not eluted ion, secondary deionized water is crossed post, and the flush away hydrochloric acid soln is neutral until crossing post liquid, repeats above-mentioned operation again.The result shows that this sorbent material has reproducibility and stability preferably in experimentation, namely can repeat post and wash-out above 20 times under the situation that does not reduce the rate of recovery (＞95 %) to Cd (II).
Embodiment 5
Extracting and enriching and the mensuration of Cd in the actual water sample (II)
Actual water sample is taken from the tap water of University of Fuzhou and each 100 mL of lake water in the school respectively.Utilize damping fluid that its pH value is adjusted to 6.5 with filtering good water sample, descended the column extracting enrichment at the best sample flow velocity, stay the ion that is not adsorbed on the post with a small amount of secondary deionized water flush away then, cross the ion that the post wash-out is adsorbed with the hydrochloric acid soln of 8 mL, 0.15 mol/L again, with the Cd (II) in the FAAS mensuration elutriant.Simultaneously, experiment is also tested water sample by adding the target method, and it is not identical that experimental technique and mark-on are tested, and adds scalar and is respectively 1.0 μ g, 2.0 μ g, and each method is parallel gathering and measuring three times all.Experimental result is as shown in table 2, and water quality meets national two class surface water standards.Actual water sample is recorded Cd (II) the ion rate of recovery between 96.0-102.0% through the mark-on experiment.
Table 2 is Cd in University of Fuzhou's tap water and the lake water (II) Determination on content results
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. cadmium ion trace preparation of adsorbent method is characterized in that: may further comprise the steps:
(1) cadmium ion and function monomer form inner complex;
(2) inner complex is cross-linked into polymkeric substance under the linking agent effect;
(3) cadmium ion forms cadmium ion trace sorbent material in the elutriant flush away polymkeric substance.
2. cadmium ion trace preparation of adsorbent method according to claim 1, it is characterized in that: concrete steps are as follows:
(1) with 1 mmol CdCl
2Be dissolved in 15 ~ 20 mL dimethyl sulfoxide (DMSO) with 2 ~ 4 mmol function monomers, solution at room temperature magnetic agitation 1 h forms the cadmium ion inner complex; Described function monomer is methacrylic acid and 4-vinylpridine, and both mol ratios are 1:1;
(2) 0.1 ~ 0.2 g Diisopropyl azodicarboxylate and 20 mmol ethylene glycol dimethacrylates are dissolved in 2 ~ 3 mL dimethyl sulfoxide (DMSO), under nitrogen protection, mix with solution in the step (1), 70 ℃ of water-bath 24 h form polymkeric substance;
(3) polymkeric substance that forms in the step (2) is used earlier washing with alcohol, removes the template cadmium ion with the washing of 2 mol/L hydrochloric acid solns subsequently, is washed till neutrality with secondary deionized water at last, the loft drier drying.
3. cadmium ion trace sorbent material that the method for claim 1 makes.
4. the application of the cadmium ion trace sorbent material that makes of the method for claim 1, it is characterized in that: this sorbent material is used for the enrichment pre-treatment of environmental water sample trace Cd (II).
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103592166A (en) * | 2013-11-14 | 2014-02-19 | 沈阳化工大学 | Method for in-situ and quantitative collection of free Cd (II) ions in water, sediment and soil environments |
| CN103630594A (en) * | 2013-11-20 | 2014-03-12 | 沈阳化工大学 | Imprint selective electrode method for detecting trace cadmium in water in real time |
| CN105148851A (en) * | 2015-09-28 | 2015-12-16 | 太原理工大学 | Preparation method and application of carbamido functionalized cadmium ion surface print adsorbent |
| CN105884985A (en) * | 2016-05-13 | 2016-08-24 | 华南农业大学 | Magnetic cadmium ion-imprinted polymer and preparation method thereof |
| CN105949389A (en) * | 2016-05-12 | 2016-09-21 | 广东省稀有金属研究所 | Preparation method of germanium ion imprinted polymer |
| CN110201646A (en) * | 2019-05-14 | 2019-09-06 | 桂林理工大学 | A kind of diatom base cadmium ion trace adsorbent and its preparation method and application |
| CN111777713A (en) * | 2020-07-23 | 2020-10-16 | 福州大学 | Metal ion coordination bifunctional monomer molecularly imprinted polymer, and preparation method and application thereof |
| CN112892496A (en) * | 2021-01-18 | 2021-06-04 | 南昌航空大学 | Preparation method of polymer adsorbent for lanthanum ions in water |
| CN114225921A (en) * | 2021-12-16 | 2022-03-25 | 中国科学院大学 | Preparation method of mercury ion imprinting adsorption material |
| CN116041618A (en) * | 2023-01-18 | 2023-05-02 | 广东工业大学 | Cadmium ion detection material and preparation method and application thereof |
| CN116288780A (en) * | 2022-12-23 | 2023-06-23 | 重庆科技学院 | Preparation method of indium ion selective separation imprinted nanofiber based on electrostatic spinning |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103592166A (en) * | 2013-11-14 | 2014-02-19 | 沈阳化工大学 | Method for in-situ and quantitative collection of free Cd (II) ions in water, sediment and soil environments |
| CN103592166B (en) * | 2013-11-14 | 2016-06-22 | 沈阳化工大学 | In situ quantitation gathers the method for free state Cd (II) ion in water, deposit, soil environment |
| CN103630594A (en) * | 2013-11-20 | 2014-03-12 | 沈阳化工大学 | Imprint selective electrode method for detecting trace cadmium in water in real time |
| CN103630594B (en) * | 2013-11-20 | 2016-01-20 | 沈阳化工大学 | A kind of method adopting Trace Cadmium in cadmium ion electrodes selective Real-Time Monitoring water |
| CN105148851A (en) * | 2015-09-28 | 2015-12-16 | 太原理工大学 | Preparation method and application of carbamido functionalized cadmium ion surface print adsorbent |
| CN105949389A (en) * | 2016-05-12 | 2016-09-21 | 广东省稀有金属研究所 | Preparation method of germanium ion imprinted polymer |
| CN105884985A (en) * | 2016-05-13 | 2016-08-24 | 华南农业大学 | Magnetic cadmium ion-imprinted polymer and preparation method thereof |
| CN110201646A (en) * | 2019-05-14 | 2019-09-06 | 桂林理工大学 | A kind of diatom base cadmium ion trace adsorbent and its preparation method and application |
| CN111777713A (en) * | 2020-07-23 | 2020-10-16 | 福州大学 | Metal ion coordination bifunctional monomer molecularly imprinted polymer, and preparation method and application thereof |
| CN112892496A (en) * | 2021-01-18 | 2021-06-04 | 南昌航空大学 | Preparation method of polymer adsorbent for lanthanum ions in water |
| CN114225921A (en) * | 2021-12-16 | 2022-03-25 | 中国科学院大学 | Preparation method of mercury ion imprinting adsorption material |
| CN114225921B (en) * | 2021-12-16 | 2024-03-19 | 中国科学院大学 | Preparation method of mercury ion imprinting adsorption material |
| CN116288780A (en) * | 2022-12-23 | 2023-06-23 | 重庆科技学院 | Preparation method of indium ion selective separation imprinted nanofiber based on electrostatic spinning |
| CN116288780B (en) * | 2022-12-23 | 2024-05-17 | 重庆科技学院 | Preparation method of indium ion selective separation imprinted nanofiber based on electrostatic spinning |
| CN116041618A (en) * | 2023-01-18 | 2023-05-02 | 广东工业大学 | Cadmium ion detection material and preparation method and application thereof |
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