CN1621146A - Silicon ball surface cadmium ion blotting mercapto group functionalized adsorption material and method for synthesis - Google Patents
Silicon ball surface cadmium ion blotting mercapto group functionalized adsorption material and method for synthesis Download PDFInfo
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- CN1621146A CN1621146A CN 200410072308 CN200410072308A CN1621146A CN 1621146 A CN1621146 A CN 1621146A CN 200410072308 CN200410072308 CN 200410072308 CN 200410072308 A CN200410072308 A CN 200410072308A CN 1621146 A CN1621146 A CN 1621146A
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- silicon ball
- cadmium ion
- mercapto
- sorbing material
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Abstract
The present invention is method of synthesizing high selectivity adsorbing material by means of molecular print technology and the advantages of silicon ball. The functional cadmium ion printed mercapto silicon ball is synthesized through activating the surface of silicon ball in methane sulfonic acid to produce active hydroxyl radical; forming complex with trimetyoxy mercapto propyl silane and cadmium ion in methanol; hydrolyzing and condensating the complex and the active silicon ball to graft the complex onto the surface of the silicon ball; and hydrochloric acid extracting to eliminate template metal ion and to obtain the functional cadmium ion printed mercapto silicon ball. The modified silicon ball as adsorbing material has special holes with very high template metal ion distinguishing capacity. The present invention has simple synthesis principle and process.
Description
[technical field]: the present invention relates to the synthetic method of pollutant sorbing material in a kind of environmental analysis, particularly a kind of synthetic method of heavy metal ion adsorbing material and sorbing material thereof.
[background technology]: fast-developing technology has been brought environmental pollution, and heavy metal ion has serious toxicological effect to the organism of living, and the ecosystem is particularly human to have brought serious threat so heavy-metal pollution is given.Cadmium is to animal and human's class one of the most virose element.Cadmium is classified as the 6th by the U.S. toxicity committee and is jeopardized the noxious material of health, is demonstrate,proved research institution by international cancer and is defined as human and the lung cancer of animal used as test and the affirmation carcinogenic substance of prostate cancer.Thereby cadmium can enter animal and human's body by the food chain system migration of soil-plant-animal-human body causes serious murder by poisoning.Therefore, the trace cadmium has important practical significance in removal and mensuration environment and the biological sample.The mensuration of trace element needs enrichment usually.Heavy metal element is removed and measured to selectivity, and SPE more has superiority and uses more extensive than traditional solvent extraction.The key of SPE development is the new solid phase adsorption material of development.Any effective sorbing material should be made up of active group and stable insoluble support.The silicon ball since have under acid condition stable, not swelling, mass transfer velocity is fast and advantage such as high temperature resistant, so the silicon ball is a desirable support.People have synthesized many sorbing materials by grafting organic functional group on the silicon ball, but the selectivity of these materials is not remarkable, because many metal ions have the ability that combines with institute grafting functional group; Moreover do not consider the spatial chemistry effect of metal ion and functional group in the building-up process of these materials, and the spatial chemistry of part is arranged and has been played the part of an important role in the identification of metal ion.
Molecular imprinting (Molecular Imprinting Technique, MIT) be one of the main method of current development high selectivity material, copy the formation mechanism of antibody exactly, around template molecule, form a highly cross-linked rigid macromolecule, in the network structure of polymer, stayed the three-dimensional hole that is complementary with template molecule size and shape after removing template molecule, the binding site that contains the recognition template molecule simultaneously in the hole is to the selection recognition performance of template guest molecule apparent altitude.Molecularly imprinted polymer is a kind of cross-linked polymer that fixed cavitation size and shape is arranged and the functional group that necessarily puts in order is arranged, and it has precordainment, identity and practicality characteristics.Molecularly imprinted polymer has represented good prospects for application in many fields such as the separating of enantiomer and position isomer, SPE, chemobionics sensor, mimetic enzyme catalysis, clinical medicine analysis, membrane separation techniques.Therefore, molecular imprinting is a kind of effective ways of preparation selective absorbent.
Molecular imprinting combines with sol-gel technique and prepares inorganic or organic-inorganic hybridized material, i.e. molecular engram sol gel film.It is exactly to have adopted conventional sol-gel process, and template molecule is combined in inorganic or inorganic-organic network, removes template molecule then, obtains selective material.In imprinted material, exist the action site of microsphere and the hole that is complementary.Compare with similar other material of structure, imprinted material has compatibility preferably to template molecule.At present, sol-gel technique is applied to the synthetic of imprinted material, and generally the method for Shi Yonging is surface imprinted method, and surface imprinted technology is an important kind of molecular imprinting, surface imprinted polymer not only has high selectivity, and has fast dynamics.Molecular imprinting and the sol-gel technique synthetic sorbing material that cadmium ion is had a high selectivity of on silicon ball surface trace sulfydryl functional group that combines is not appeared in the newspapers so far.
[summary of the invention]: purpose of the present invention solves existing silicon ball sorbing material poor selectivity exactly, and do not consider the problem of the spatial chemistry effect of metal ion and functional group in the building-up process, providing a kind of combines molecular imprinting and sol-gel technique, trace sulfydryl functional group on silicon ball surface, synthetic have high method and the sorbing material thereof of selecting sorbing material to cadmium ion.
At first:, can not satisfy the needs that silicon ball surface is modified, so must activate to silicon ball surface because commercial silicon ball surface activity hydroxy is few.Because Loprazolam is an acid catalyst that catalytic capability is very strong, the boiling point height is non-volatile and reusable, so use Loprazolam to make catalyst silicon ball surface is activated.
Second: trimethoxy mercaptopropylsilane and cadmium ion form complex compound in methyl alcohol, add to have activated the silicon ball again.The condensation that is hydrolyzed together in methyl alcohol of complex compound and activation silicon ball makes the complex compound grafting on silicon ball surface.
The 3rd: above-mentioned product is washed with ethanol, and the salt acid soak is removed unreacted trimethoxy mercaptopropylsilane and templated metal ion respectively, and is dry in a vacuum, must have the high material of selecting absorption to cadmium ion.
Its concrete building-up process is as follows:
The activation of silicon ball: it is in 5%～90%50～80ml Loprazolam aqueous solution that 4～10g silicon ball is added to concentration, stirring and refluxing 4～8h leaches solid, and it is neutral washing repeatedly to water lotion with distilled water, in 70～80 ℃ of vacuum drying 12～24h, must activate the silicon ball..
The preparation of the mercapto-functionalized silicon ball of cadmium ion trace: with CdCl
22.5H
2O adds in the methyl alcohol, and the consumption of methyl alcohol is for making CdCl
2Just dissolving, agitating heating makes CdCl
2After the dissolving, add CdCl fully
2The trimethoxy mercaptopropylsilane of twice molal quantity behind the reaction backflow 1h, adds activation silicon ball, and the trimethoxy mercaptopropylsilane is 1ml: 1.4～1.5g with the ratio of activation silicon ball, continues the 18～22h that refluxes; Leach solid,, remove unreacted trimethoxy mercaptopropylsilane, use 6molL with the ethanol washing
-1Hydrochloric acid stirs and soaks 2h, and suction filtration is removed the templated metal ion, is washed till washing lotion pH4～5,70～80 ℃ vacuum drying 10～12h with secondary deionized water, gets the mercapto-functionalized silicon ball of cadmium ion trace.
The mercapto-functionalized sorbing material of a kind of silicon ball surface cadmium ion trace is the mercapto-functionalized silicon ball of cadmium ion trace that combines the sulfydryl grafting is made on silicon ball surface by engram technology and sol-gel technique.
Advantage of this method and effect: this method is utilized the sorbing material of the synthetic high selectivity of advantage of molecular imprinting and silicon ball inherence.Be that silicon ball surface is activated the generation activity hydroxy; The trimethoxy mercaptopropylsilane and the cadmium ion that contain bifunctional group form complex compound; Complex compound and activation silicon ball be hydrolytic condensation together, with the complex compound grafting on silicon ball surface, through hcl as extraction agent the templated metal ion is removed, stayed special hole on modification silicon ball, this special hole has very high recognition capability to the templated metal ion.Composition principle of this method and building-up process are very simple; Used instrument and equipment is conventional equipment, as: electric mixer, thermal source, three-necked bottle, reflux condensing tube and thermometer, its production cost is low; Reaction condition is simple, adds hot reflux and gets final product, and does not have the exacting terms requirement.The material that is synthesized has high selectivity to cadmium ion.
[specific embodiment]: the mercapto-functionalized absorption silicon of cadmium ion trace ball synthetic:
The activation of silicon ball: in the 250ml three-necked bottle of electric mixer, reflux condensing tube and thermometer is housed, add 8g 80～120 order silicon balls, 1: 2 (v/v) Loprazolam of 60ml aqueous solution, stirring and refluxing 6h.Leach solid, it is neutral washing repeatedly to water lotion with distilled water, in 70 ℃ of vacuum drying 20h.
The preparation of the mercapto-functionalized silicon ball of cadmium ion trace: take by weighing 1.92g CdCl
22.5H
2O adds 80ml methyl alcohol in the 250ml three-necked bottle, electronic agitating heating makes CdCl
2Dissolving fully adds 4ml trimethoxy mercaptopropylsilane, behind the reaction backflow 1h, adds 6g activation silicon ball, continues backflow 20h.Leach solid,, transfer in the 100ml conical flask, add 50ml 6molL with the ethanol washing
-1Hydrochloric acid stirs and soaks 2h, and suction filtration is washed till washing lotion pH4～5,80 ℃ vacuum drying 10h with secondary deionized water, gets the mercapto-functionalized silicon ball of cadmium ion trace, i.e. sorbing material.This material has the high adsorption capacity of selecting to cadmium ion.
Other embodiment referential datas, see the following form:
The activation of table 1, silicon ball
| The silicon ball | The Loprazolam aqueous solution | Stirring and refluxing | Baking temperature | Drying time |
| 6g | ?50ml?1∶1(v/v) | 6h | ?70℃ | 12h |
| 10g | ?80ml?2∶1(v/v) | 5h | ?80℃ | 16h |
The preparation of table 2, the mercapto-functionalized silicon ball of cadmium ion trace
| CdCl 2·2.5H 2O | Methyl alcohol | The trimethoxy mercaptopropylsilane | Activation silicon ball | Reflux | Hydrochloric acid | Baking temperature | Drying time |
| 0.96g | ?50ml | ?2ml | ?2.8g | ?18h | ?40ml | ?70℃ | 10h |
| 2.88g | ?120ml | ?6ml | ?9g | ?22h | ?60ml | ?80℃ | 10h |
Claims (4)
1, the synthetic method of the mercapto-functionalized sorbing material of a kind of silicon ball surface cadmium ion trace is characterized in that this method finishes by following steps:
A. the silicon ball activates in Loprazolam;
B. the trimethoxy mercaptopropylsilane forms complex compound with cadmium ion in methyl alcohol;
C. the condensation that is hydrolyzed of the complex compound in the activation silicon ball in a step being gone on foot with b;
D. hcl as extraction agent is removed the templated metal ion, makes the sorbing material that cadmium ion is had high selectivity.
2, the synthetic method of sorbing material according to claim 1, the activation that it is characterized in that the silicon ball is: it is 5%～90% that 4～10g silicon ball is added to concentration, in the Loprazolam aqueous solution of 50～80ml, stirring and refluxing 4～8h, leach solid, it is neutral washing repeatedly to water lotion with distilled water, in 70～80 ℃ of vacuum drying 12～24h, must activate the silicon ball.
3, the synthetic method of sorbing material according to claim 1 and 2 is characterized in that complex compound forms and the hydrolytic condensation process is: with CdCl
22.5H
2O adds in the methyl alcohol, and the consumption of methyl alcohol is for making CdCl
2Just dissolving, agitating heating makes CdCl
2After the dissolving, add CdCl fully
2The trimethoxy mercaptopropylsilane of twice molal quantity behind the reaction backflow 1h, adds activation silicon ball, and the trimethoxy mercaptopropylsilane is 1ml: 1.4～1.5g with the ratio of activation silicon ball, continues the 18～22h that refluxes; Leach solid,, remove unreacted trimethoxy mercaptopropylsilane, use 6mol L with the ethanol washing
-1Hydrochloric acid stirs and soaks 2h, and suction filtration is removed the templated metal ion, is washed till washing lotion pH4～5,70～80 ℃ vacuum drying 10～12h with secondary deionized water, gets the mercapto-functionalized silicon ball of cadmium ion trace.
4, the mercapto-functionalized sorbing material of a kind of silicon ball surface cadmium ion trace is characterized in that the mercapto-functionalized silicon ball of cadmium ion trace that combines the sulfydryl grafting is made by engram technology and sol-gel technique on silicon ball surface.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811032A (en) * | 2010-04-02 | 2010-08-25 | 同济大学 | Preparation and application methods of Cd (II) imprinted magnetic material |
| CN101091911B (en) * | 2007-04-16 | 2010-12-15 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
| 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 |
| CN110270313A (en) * | 2019-06-26 | 2019-09-24 | 江苏大学 | Vapor condensing method prepares the method and its application of silicon ball and functionalization silicon ball adsorbent |
-
2004
- 2004-10-10 CN CN 200410072308 patent/CN1621146A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091911B (en) * | 2007-04-16 | 2010-12-15 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
| CN101811032A (en) * | 2010-04-02 | 2010-08-25 | 同济大学 | Preparation and application methods of Cd (II) imprinted magnetic material |
| CN101811032B (en) * | 2010-04-02 | 2012-11-07 | 同济大学 | Preparation and application methods of Cd (II) imprinted magnetic material |
| 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 |
| CN110270313A (en) * | 2019-06-26 | 2019-09-24 | 江苏大学 | Vapor condensing method prepares the method and its application of silicon ball and functionalization silicon ball adsorbent |
| CN110270313B (en) * | 2019-06-26 | 2021-12-21 | 江苏大学 | Method for preparing silicon spheres and functional silicon sphere adsorbent by steam condensation method and application thereof |
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