CN109351347A - It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer - Google Patents

It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer Download PDF

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Publication number
CN109351347A
CN109351347A CN201811138597.0A CN201811138597A CN109351347A CN 109351347 A CN109351347 A CN 109351347A CN 201811138597 A CN201811138597 A CN 201811138597A CN 109351347 A CN109351347 A CN 109351347A
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hexavalent chromium
composite membrane
acrylamide
function monomer
trace composite
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Inventor
字富庭
刘迎梅
胡德琼
陈树梁
王朝武
陈云龙
何易
成会玲
胡显智
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/268Polymers created by use of a template, e.g. molecularly imprinted polymers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer, belongs to heavy metal ion adsorbed separation technology field.Using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer, use hexavalent chromium for template ion, acrylamide is function monomer, ethylene glycol dimethacrylate is crosslinking agent, azodiisobutyronitrile is initiator, it is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, hexavalent chromium trace composite membrane is prepared on support membrane by surface grafting method.The present invention is using existing commercial membranes as support membrane, hexavalent chromium trace composite membrane is prepared using metal ion engram technology, it is simple without complex operations, the preparation method such as grinding or sieving, strong environmental adaptability can be used for the adsorbing separation containing hexavalent chromium in Cr(VI) solution.

Description

It is a kind of using acrylamide as the preparation of the hexavalent chromium trace composite membrane of function monomer Method and application
Technical field
The present invention relates to a kind of using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer and Using belonging to heavy metal ion adsorbed separation technology field.
Background technique
As the fast-developing chromium and compound of human economy is widely used in plating, medal polish, leather tanning, weaving The industries such as product dyeing, cause serious pollution.In all valence states of chromium, trivalent chromium and Cr VI stable in nature can be deposited Wherein a small amount of trivalent chromium is microelement necessary to life entity, and Cr VI is then carcinogen, the experiment proved that it is malicious Property is more than 100 times of trivalent chromium, will lead to the major diseases such as lung cancer, liver cancer, therefore, the elimination of hexavalent chromium has in water body Critically important meaning.Hexavalent chromium is different from other heavy metal ion, in water body according to environment it is different mainly with Cr2O7 2-、HCrO4-、CrO4 2-The form of anion exists, and it is larger to remove difficulty for it compared with other heavy metal ion.
Currently, hexavalent chromium removing method mainly have membrane separation process, electrolysis method, chemical precipitation method, ion-exchange and Absorption method etc., wherein absorption method is most common method, has many advantages, such as high efficiency, low cost and easy to operate, but conventional is inhaled Attached method is unfavorable for the specific recognition of specific ion, can increase the difficulty that the later period separates again.In view of hexavalent chromium polluted severe shape Gesture, finding a kind of effective hexavalent chromium processing method becomes and its important.Metal ion engram technology is a kind of improves specially Using special metal ion as template organic small point of chelation can occur with metal ion for the method for one property recognition capability Son is function monomer, forms a kind of imprinted material under the action of crosslinking agent and initiator, elution remove leave after template with The identical hole of template molecule space size, so that specific recognition is carried out to special metal ion, in view of this feature metal Ionic imprinting technique is widely used in the adsorbing separation field of heavy metal ion.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of using acrylamide as function monomer The preparation method and application of hexavalent chromium trace composite membrane.The present invention utilizes metal ion using existing commercial membranes as support membrane Engram technology prepares hexavalent chromium trace composite membrane, and without the complex operations such as grinding or sieving, preparation method is simple, and environment is suitable Should be able to power it is strong, can be used for containing Cr(VI) adsorbing separation of hexavalent chromium in solution.
The present invention uses hexavalent chromium for template ion, and acrylamide is function monomer, ethyleneglycol dimethacrylate Ester is crosslinking agent, and azodiisobutyronitrile is initiator, and commercially available commercial membranes are support membrane, with the mixed of You machine Rong Ji ∕ water (v:v=1:1) Conjunction solution is porogenic solvents, and hexavalent chromium trace composite membrane is prepared on support membrane with surface grafting method.This method institute Commercial membranes are stated under porogenic solvents, the nitrogenous small organic molecule of chelation can be generated with metal ion in its area load, Under the action of crosslinking agent and initiator, ion blotting composite membrane is formed in film surface cross-linked polymeric, after elution removes template ion, Film surface forms the hole for having specific recognition to template ion, to obtain having high adsorbing separation energy to hexavalent chromium The trace composite membrane of power.
It is a kind of using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer, using Cr VI from Son is template ion, and acrylamide is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is to draw Agent is sent out, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, through surface grafting method on support membrane Hexavalent chromium trace composite membrane is prepared, the specific steps are as follows:
Step 1, by K2Cr2O7It is dissolved in the organic solvent and water mixed solution porogenic solvents that volume ratio is 1:1, adds propylene Amide function monomer, isothermal vibration reacts 2~3 h at room temperature, and ethylene glycol dimethacrylate and two isobutyl of azo is added Nitrile is dissolved and is shaken up, and forms pre-polymerization liquid;
Support membrane is placed in the pre-polymerization liquid in step 1 by step 2, is impregnated 3~60 min at normal temperature, is then heated to 60~80 12~24 h are reacted at DEG C, the methanol for being finally 9:1 with volume ratio and the elution of acetic acid mixed solution remove template ion, are prepared into To hexavalent chromium trace composite membrane.
K in the step 12Cr2O7, acrylamide and ethylene glycol dimethacrylate molar ratio be 1:2~8:10~ 50。
Organic solvent is methanol, ethyl alcohol, acetonitrile, N-N- dimethylformamide or isopropanol in the step 1.
Support membrane is polytetrafluoroethylene (PTFE) miillpore filter, polyvinylidene fluoride microporous filtering film and Nylon-6 micropore in the step 2 Filter membrane.Above-mentioned support membrane is commercially available commercial membranes.
A kind of hexavalent chromium trace composite membrane applies the adsorbing separation of hexavalent chromium in the solution.
The beneficial effects of the present invention are:
(1) the method for the present invention is used based on the principle for having preferable chelation between hexavalent chromium and nitrogenous small organic molecule Commercially available commercial membranes are support membrane, overcome the disadvantages of existing hexavalent chromium imprinted polymer preparation is difficult, and method is cumbersome.
(2) trace composite membrane prepared by can hexavalent chromium effectively in adsorbent solution, imprinting effect is good.
(3) the trace composite membrane has many advantages, such as that stability is good using acrylamide as function monomer, and preparation method is simple, It can be used for the adsorbing separation containing hexavalent chromium in Cr (VI) solution.
Specific embodiment
With reference to embodiment, the invention will be further described.
This is using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer, using hexavalent chromium For template ion, acrylamide is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is to cause Agent is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is made on support membrane by surface grafting method It is standby to obtain hexavalent chromium trace composite membrane, the specific steps are as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (methanol) and water mixed solution pore of 10mL, volume ratio for 1:1 In solvent, acrylamide function monomer is added, isothermal vibration reacts 2 h at room temperature, and ethyleneglycol dimethacrylate is added Ester and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid;Wherein K2Cr2O7, acrylamide and ethylene glycol dimethyl propylene Acid esters molar ratio is 1:2:10;K2Cr2O7It is 1:0.6 with azodiisobutyronitrile molar ratio;
Support membrane (polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, impregnates 3min at normal temperature, so After be warming up at 60 DEG C and react 12 h, the methanol for being finally 9:1 with 150 mL, volume ratio and the elution of acetic acid mixed solution remove mould Hexavalent chromium trace composite membrane is prepared in plate ion.
The 1.95g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration In 0.24 mmol/L solution, adsorbance is 41.31 μm of ol/g, imprinting factor 1.16.
Embodiment 2
This uses hexavalent chromium for mould using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer Plate ion, acrylamide are function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, It is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is prepared on support membrane by surface grafting method Obtain hexavalent chromium trace composite membrane, the specific steps are as follows:
Step 1, by 0.1mmo K2Cr2O7It is dissolved in 10 mL, the organic solvent (ethyl alcohol) that volume ratio is 1:1 and water mixed solution cause In the solvent of hole, acrylamide function monomer is added, isothermal vibration reacts 3 h at room temperature, and ethylene glycol dimethyl propylene is added Acid esters and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid;Wherein K2Cr2O7, acrylamide and ethylene glycol dimethyl third Olefin(e) acid ester molar ratio is 1:4:20;K2Cr2O7It is 1:0.8 with azodiisobutyronitrile molar ratio;
Support membrane (polyvinylidene fluoride microporous filtering film) is placed in the pre-polymerization liquid in step 1 by step 2, impregnates 3 min at normal temperature, It then heats at 60 DEG C and reacts 24 h, the methanol for being finally 9:1 with 150 mL, volume ratio and the elution of acetic acid mixed solution remove Hexavalent chromium trace composite membrane is prepared in template ion.
The 1.91g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration In 0.24 mmol/L solution, adsorbance is 25.65 μm of ol/g, imprinting factor 1.10.
Embodiment 3
This uses hexavalent chromium for mould using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer Plate ion, acrylamide are function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, It is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is prepared on support membrane by surface grafting method Obtain hexavalent chromium trace composite membrane, the specific steps are as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in 10 mL, the organic solvent (acetonitrile) that volume ratio is 1:1 and water mixed solution cause In the solvent of hole, acrylamide function monomer is added, isothermal vibration reacts 3h at room temperature, and ethyleneglycol dimethacrylate is added Ester and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid;Wherein K2Cr2O7, acrylamide and ethylene glycol dimethyl propylene Acid esters molar ratio is 1:4:30;K2Cr2O7It is 1:1 with azodiisobutyronitrile molar ratio;
Support membrane (Nylon-6 miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, impregnates 3min at normal temperature, then It is warming up at 60 DEG C and reacts 24 h, the methanol for being finally 9:1 with 150 mL, volume ratio and the elution of acetic acid mixed solution remove template Hexavalent chromium trace composite membrane is prepared in ion.
The 1.95g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration In 0.24 mmol/L solution, adsorbance is 25.65 μm of ol/g, imprinting factor 1.10.
Embodiment 4
This uses hexavalent chromium for mould using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer Plate ion, acrylamide are function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, It is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is prepared on support membrane by surface grafting method Obtain hexavalent chromium trace composite membrane, the specific steps are as follows:
Step 1, by 0.1mmol K2Cr2O7Be dissolved in 10 mL, volume ratio be 1:1 organic solvent (N-N- dimethylformamide) and In water mixed solution porogenic solvents, acrylamide function monomer is added, isothermal vibration reacts 3 h at room temperature, and second two is added Alcohol dimethylacrylate and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid;Wherein K2Cr2O7, acrylamide and second Diol dimethacrylate molar ratio is 1:6:40;K2Cr2O7It is 1:1.2 with azodiisobutyronitrile molar ratio;
Support membrane (Nylon-6 miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, impregnates 60 min at normal temperature, so After be warming up at 80 DEG C and react 36 h, the methanol for being finally 9:1 with 150 mL, volume ratio and the elution of acetic acid mixed solution remove Hexavalent chromium trace composite membrane is prepared in template ion.
The 1.92g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration In 0.24 mmol/L solution, adsorbance is 45.37 μm of ol/g, imprinting factor 1.33.
Embodiment 5
This uses hexavalent chromium for mould using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer Plate ion, acrylamide are function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiator, It is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is prepared on support membrane by surface grafting method Obtain hexavalent chromium trace composite membrane, the specific steps are as follows:
Step 1, by 0.1mmol K2Cr2O7It is dissolved in 10 mL, the organic solvent (isopropanol) and water mixed solution that volume ratio is 1:1 In porogenic solvents, acrylamide function monomer is added, isothermal vibration reacts 2.5 h at room temperature, and ethylene glycol dimethyl is added Acrylate and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid;Wherein K2Cr2O7, acrylamide and glycol dinitrate Base acrylate molar ratio is 1:8:50;K2Cr2O7It is 1:1.2 with azodiisobutyronitrile molar ratio;
Support membrane (Nylon-6 miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, impregnates 30 min at normal temperature, so After be warming up at 70 DEG C and react 24 h, the methanol for being finally 9:1 with 150 mL, volume ratio and the elution of acetic acid mixed solution remove Hexavalent chromium trace composite membrane is prepared in template ion.
The 1.95g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration In 0.24 mmol/L solution, adsorbance is 43.73 μm of ol/g, imprinting factor 1.33.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art Various change out.

Claims (5)

1. a kind of using acrylamide as the preparation method of the hexavalent chromium trace composite membrane of function monomer, it is characterised in that: adopt It is template ion with hexavalent chromium, acrylamide is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, azo two Isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, passes through surface grafting method Hexavalent chromium trace composite membrane is prepared on support membrane, the specific steps are as follows:
Step 1, by K2Cr2O7It is dissolved in the organic solvent and water mixed solution porogenic solvents that volume ratio is 1:1, adds propylene Amide function monomer, isothermal vibration reacts 2~3 h at room temperature, and ethylene glycol dimethacrylate and two isobutyl of azo is added Nitrile is dissolved and is shaken up, and forms pre-polymerization liquid;
Support membrane is placed in the pre-polymerization liquid in step 1 by step 2, is impregnated 3~60 min at normal temperature, is then heated to 60~80 12~36 h are reacted at DEG C, the methanol for being finally 9:1 with volume ratio and the elution of acetic acid mixed solution remove template ion, are prepared into To hexavalent chromium trace composite membrane.
2. according to claim 1 using acrylamide as the preparation side of the hexavalent chromium trace composite membrane of function monomer Method, it is characterised in that: K in the step 12Cr2O7, acrylamide and ethylene glycol dimethacrylate molar ratio be 1:2~8: 10~50.
3. according to claim 1 using acrylamide as the preparation side of the hexavalent chromium trace composite membrane of function monomer Method, it is characterised in that: organic solvent is methanol, ethyl alcohol, acetonitrile, N-N- dimethylformamide or isopropanol in the step 1.
4. according to claim 1 using acrylamide as the preparation side of the hexavalent chromium trace composite membrane of function monomer Method, it is characterised in that: in the step 2 support membrane be polytetrafluoroethylene (PTFE) miillpore filter, polyvinylidene fluoride microporous filtering film and Nylon-6 miillpore filter.
5. a kind of hexavalent chromium trace composite membrane according to any one of claims 1 to 4 is using sexavalence in the solution The adsorbing separation of chromium ion.
CN201811138597.0A 2018-09-28 2018-09-28 It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer Pending CN109351347A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438619A (en) * 2018-09-28 2019-03-08 昆明理工大学 It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer
CN110339731A (en) * 2019-07-02 2019-10-18 昆明理工大学 A kind of preparation method and applications of chromium (VI) ion blotting composite membrane
CN115212855A (en) * 2022-07-04 2022-10-21 广东食品药品职业学院 Molecularly imprinted membrane and preparation method and application thereof
CN116084048A (en) * 2022-12-30 2023-05-09 重庆科技学院 Preparation method of chromium ion selective separation imprinting nanofiber based on electrostatic spinning
CN116084048B (en) * 2022-12-30 2024-07-02 重庆科技学院 Preparation method of chromium ion selective separation imprinting nanofiber based on electrostatic spinning

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CN102507515A (en) * 2011-09-27 2012-06-20 浙江工业大学 Fluorescent ion imprint sensor for detection of cadmium ions and preparation method thereof
CN105771701A (en) * 2014-12-23 2016-07-20 中国石油化工股份有限公司 Preparation method for metal ion-imprinted composite film
CN106256839A (en) * 2015-06-18 2016-12-28 中国石油化工股份有限公司 A kind of method that ion blotting composite membrane is prepared in surface heat polymerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102507515A (en) * 2011-09-27 2012-06-20 浙江工业大学 Fluorescent ion imprint sensor for detection of cadmium ions and preparation method thereof
CN105771701A (en) * 2014-12-23 2016-07-20 中国石油化工股份有限公司 Preparation method for metal ion-imprinted composite film
CN106256839A (en) * 2015-06-18 2016-12-28 中国石油化工股份有限公司 A kind of method that ion blotting composite membrane is prepared in surface heat polymerization

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438619A (en) * 2018-09-28 2019-03-08 昆明理工大学 It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer
CN110339731A (en) * 2019-07-02 2019-10-18 昆明理工大学 A kind of preparation method and applications of chromium (VI) ion blotting composite membrane
CN115212855A (en) * 2022-07-04 2022-10-21 广东食品药品职业学院 Molecularly imprinted membrane and preparation method and application thereof
CN115212855B (en) * 2022-07-04 2024-04-12 广东食品药品职业学院 Molecularly imprinted membrane and preparation method and application thereof
CN116084048A (en) * 2022-12-30 2023-05-09 重庆科技学院 Preparation method of chromium ion selective separation imprinting nanofiber based on electrostatic spinning
CN116084048B (en) * 2022-12-30 2024-07-02 重庆科技学院 Preparation method of chromium ion selective separation imprinting nanofiber based on electrostatic spinning

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