CN117089020A - Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material - Google Patents

Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material Download PDF

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CN117089020A
CN117089020A CN202311102540.6A CN202311102540A CN117089020A CN 117089020 A CN117089020 A CN 117089020A CN 202311102540 A CN202311102540 A CN 202311102540A CN 117089020 A CN117089020 A CN 117089020A
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CN117089020B (en
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成会玲
罗甘滨
付冬雪
洪玉文
赵莉
杨朋
字富庭
胡显智
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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
    • B01J20/22Solid 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
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/02Characterised by the use of homopolymers or copolymers of esters

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Materials Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a nano TiO-based material 2 The preparation method of Co (II) ion imprinting adsorption material belongs to the technical field of adsorption separation of surface ion imprinting material. The preparation method comprises the following steps: co (II) ions are used as template ions, bis (2, 4-trimethyl amyl) phosphinic acid is used as ligand, alpha-methacrylic acid is used as functional monomer, and nano TiO (titanium dioxide) 2 As a carrier, ethylene glycol dimethacrylate as a cross-linking agent and azobisisobutyronitrile as a primerA hair-growing agent; co (II) ion imprinted polymer was synthesized by thermal initiation surface imprinting technique at 60℃for 12h. The invention prepares the Co (II) ion surface imprinted polymer by utilizing the characteristic that the surface ion imprinted polymer has high selectivity to template ions, has simple preparation process and realizes specific identification and effective separation of Co (II) ions.

Description

Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material
Technical Field
The invention relates to a nano TiO-based material 2 The preparation method of Co (II) ion imprinting adsorption material belongs to the technical field of adsorption separation of surface ion imprinting material.
Background
With the development of industry, a large amount of Co (II) is discharged into the environment, and Co (II) ions are used as a nutrient substance at a low concentration, and are beneficial to human beings and plants. Whereas when Co (II) ions exceed a certain concentration, various acute or chronic reactions may be caused, such as reactions affecting the gastrointestinal tract, asthma, pneumonia, etc. Therefore, it is particularly important to effectively treat and remove Co (II) ions in wastewater. At present, the main methods for removing the cobalt-containing wastewater include an electrochemical method, a chemical precipitation method and an adsorption method. However, these methods have certain disadvantages, such as complex process, high cost, poor selectivity and easy secondary pollution. It is therefore desirable to find a method that can efficiently separate Co (II) ions.
The ion imprinting technology is developed on the basis of the molecular imprinting technology, and is an effective method for preparing the adsorption material with specific selectivity to target ions, because adsorption vacancies which are highly matched with the charge number, radius and space structure of the template ions can be formed in the way, so that good selectivity to the target ions can be shown. However, the ion-imprinted polymer obtained by the traditional precipitation polymer method often has the problems that specific recognition sites are buried, template ions are difficult to elute, and the like, so that the selectivity of the polymer is reduced.
To overcome these disadvantages, it is necessary to control the template ions to the surface of the materialIn order to obtain more effective recognition sites, template ions enter the imprinting holes better. Thus, surface ion imprinting techniques have been greatly developed. The imprinting holes are positioned on the surface of the polymer thin layer, so that not only is the template ions easy to elute, but also more binding sites are formed on the surface to be combined with the template ions, and faster binding kinetics can be obtained. Currently, due to different application requirements, many types of inorganic materials are used as support substrates for surface imprinting techniques (e.g., siO 2 Silica gel, al 2 O 3 、TiO 2 Carbon nanotubes, cdS, znS quantum dots, etc.). In addition, nano TiO 2 As a novel inorganic material, the material has a plurality of excellent performances such as innocuity, low cost, light stability, stable chemical property, high efficiency of photocatalysis effect and the like. Therefore, we choose TiO 2 Nanoparticles were studied as support matrices.
Disclosure of Invention
The invention provides a nano TiO-based material 2 The preparation method of the Co (II) ion imprinting adsorption material synthesizes a novel Co (II) ion imprinting material through a surface ion imprinting technology. The preparation method is simple, and the obtained ion imprinting adsorption material realizes effective separation of Co (II) ions. The invention is realized by the following technical methods:
(1) Cobalt ion compound CoCl in a ratio of 0.005mmol/mL 2 ·6H 2 O is dissolved in a pore-forming solvent, and ligand bis (2, 4-trimethylpentyl) phosphinic acid is added according to the proportion of 0.015mmol/mL for reaction for 1h.
(2) The functional monomer alpha-methacrylic acid is added in a proportion of 0.02mmol/mL and is oscillated for 2h at 25 ℃.
(3) Adding the carrier nano TiO according to the proportion of 1.25mg/mL 2 Adding crosslinking agent glycol dimethacrylate at a ratio of (0.05-0.25) mmol/mL, adding initiator azobisisobutyronitrile at a ratio of 1mg/mL, performing ultrasonic treatment for 10min to form uniform solution, and introducing N 2 Removing oxygen in the solution for 5min, and polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.2mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
Preferably, the reaction time in step (1) is 1h.
Preferably, the reaction conditions in step (2) are shaking at 25℃for 2h.
Preferably, the conditions for uniform mixing in the step (3) are as follows: and (5) carrying out ultrasonic treatment for 10min.
Preferably, the reaction conditions in step (3) are polymerization at 60℃for 12 hours.
Preferably, the molar ratio of Co (II) ions, ligand, functional monomer and crosslinking agent in step (1) is 1:3:4 (10-50).
Preferably, the pore-forming agent used in the step (1) is a mixed solution of methanol and water, wherein the volume ratio of the methanol to the water is 1:1.
The beneficial effects of the invention are that
(1) The invention relates to a nano TiO based material 2 The preparation method of the Co (II) ion imprinting adsorption material is relatively simple, the required reagents and instruments are more conventional, the operation is easy, and the cost is low.
(2) Through the participation of the ligand and the combination of the surface ion imprinting technology, the specific recognition sites can be increased, and the selectivity of the imprinting material can be improved.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the above.
Example 1
Based on nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl was added 2 ·6H 2 O was dissolved in 20mL of methanol/water at a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added for reaction for 1h.
(2) 0.40mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) Adding 20.00mg of carrier nano TiO 2 1.00mmol of cross-linking agent glycol dimethacrylate, 20.00mg of initiator azo-bis-isobutyronitrile, and then ultrasonic treatment for 10min to form a uniform solution, and introducing N 2 Oxygen in the solution was removed for 5 min. Polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.20mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
20.00mg of Co (II) ion imprinting material prepared by the experiment is applied to a solution with the concentration of Co (II) ions of 12.31mg/mL for adsorption.
The results show that: the adsorption capacity of the Co (II) ion imprinting material is 132.19mg/g, and the imprinting factor is 1.30.
Example 2
Based on nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl was added 2 ·6H 2 O was dissolved in 20mL of methanol/water at a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added for reaction for 1h.
(2) 0.40mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) Adding 20.00mg of carrier nano TiO 2 2.00mmol of cross-linking agent glycol dimethacrylate, 20.00mg of initiator azo-bis-isobutyronitrile, and then ultrasonic treatment for 10min to form a uniform solution, and introducing N 2 Removing oxygen in the solution for 5 min; polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.20mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
20.00mg of Co (II) ion imprinting material prepared by the experiment is applied to a solution with the concentration of Co (II) ions of 12.31mg/mL for adsorption.
The results show that: the adsorption capacity of the Co (II) ion imprinting material is 158.70mg/g, and the imprinting factor is 2.35.
Example 3
Based on nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl was added 2 ·6H 2 O was dissolved in 20mL of methanol/water at a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added for reaction for 1h.
(2) 0.40mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) Adding 20.00mg of carrier nano TiO 2 3.00mmol of cross-linking agent glycol dimethacrylate, 20.00mg of initiator azodiisobutyronitrile, and then ultrasonic for 10min to form a uniform solution, and introducing N 2 Oxygen in the solution was removed for 5 min. Polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.20mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
20.00mg of Co (II) ion imprinting material prepared by the experiment is applied to a solution with the concentration of Co (II) ions of 12.31mg/mL for adsorption.
The results show that: the adsorption capacity of the Co (II) ion imprinting material is 176.30mg/g, and the imprinting factor is 1.36.
Example 4
Based on nanometer TiO 2 The specific steps of the preparation method of the Co (II) ion imprinting adsorption material are as follows;
(1) 0.10mmol of cobalt ion compound CoCl was added 2 ·6H 2 O was dissolved in 20mL of methanol/water at a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added for reaction for 1h.
(2) 0.40mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) Adding 20.00mg of carrier nano TiO 2 4.00mmol crosslinkerEthylene glycol dimethacrylate, initiator azodiisobutyronitrile 20.00mg, and ultrasonic treatment for 10min to form homogeneous solution, introducing N 2 Oxygen in the solution was removed for 5 min. Polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.20mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
20.00mg of Co (II) ion imprinting material prepared by the experiment is applied to a solution with the concentration of Co (II) ions of 12.31mg/mL for adsorption.
The results show that: the adsorption capacity of the Co (II) ion imprinting material is 206.63mg/g, and the imprinting factor is 1.88.
Example 5
Based on nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl was added 2 ·6H 2 O was dissolved in 20mL of methanol/water at a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added for reaction for 1h.
(2) 0.40mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) Adding 20.00mg of nano-carrier TiO 2 5.00mmol of cross-linking agent glycol dimethacrylate, 20.00mg of initiator azodiisobutyronitrile, and then ultrasonic for 10min to form a uniform solution, and introducing N 2 Removing oxygen in the solution for 5 min; polymerizing for 12h at 60 ℃ to obtain the Co (II) ion imprinted polymer.
(4) The polymer is filtered, and 0.20mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
20.00mg of Co (II) ion imprinting material prepared by the experiment is applied to a solution with the concentration of Co (II) ions of 12.31mg/mL for adsorption.
The results show that: the adsorption capacity of the Co (II) ion imprinting material is 123.9mg/g, and the imprinting factor is 1.11.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (7)

1. Based on nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of:
(1) Cobalt ion compound CoCl in a ratio of 0.005mmol/mL 2 ·6H 2 O is dissolved in a pore-forming solvent, and ligand bis (2, 4-trimethylpentyl) phosphinic acid is added according to the proportion of 0.015mmol/mL for reaction;
(2) Adding a functional monomer alpha-methacrylic acid according to the proportion of 0.02 mmol/mL;
(3) Adding the carrier nano TiO according to the proportion of 1.25mg/mL 2 Adding cross-linking agent glycol dimethacrylate according to the proportion of 0.05-0.25mmol/mL, adding initiator azo-bis-isobutyronitrile according to the proportion of 1mg/mL, mixing uniformly, and introducing N 2 Removing oxygen in the solution for 5min, and obtaining Co (II) ion imprinted polymer after the reaction is completed;
(4) The polymer is filtered, and 0.2mol/L EDTA is used for removing Co (II) ions in the polymer, so that the Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has three-dimensional cavities is finally obtained.
2. nano-TiO based according to claim 1 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: the reaction time in step (1) was 1h.
3. nano-TiO based according to claim 1 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: the reaction conditions in step (2) were shaking at 25℃for 2h.
4. Based on claim 1Nanometer TiO 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: the conditions for uniform mixing in the step (3) are as follows: and (5) carrying out ultrasonic treatment for 10min.
5. nano-TiO based according to claim 1 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: the reaction condition in the step (3) is that the polymerization is carried out for 12 hours at 60 ℃.
6. nano-TiO based according to claim 1 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: in the step (1), the mol ratio of Co (II) ions, ligand, functional monomer and crosslinking agent is 1:3:4 (10-50).
7. A nano-TiO-based according to claim 1 2 The preparation method of the Co (II) ion imprinting adsorption material is characterized by comprising the following steps of: the pore-forming agent used in the step (1) is a mixed solution of methanol and water, wherein the volume ratio of the methanol to the water is 1:1.
CN202311102540.6A 2023-08-30 Based on nanometer TiO2Preparation method of Co (II) ion imprinting adsorption material Active CN117089020B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259229A (en) * 1979-05-16 1981-03-31 Nikitin Jury E Process for producing colored polymer
US20070191551A1 (en) * 2006-02-16 2007-08-16 Sungkyunkwan University Foundation For Corporate Collaboration Selective separation of heavy metal ion using metal ion imprinted polymer (MMIP)
CN104804134A (en) * 2014-01-26 2015-07-29 北京林业大学 Preparation method and application of isorhamnetin surface molecularly imprinted microsphere based on nanometer titanium dioxide
CN104804152A (en) * 2014-01-26 2015-07-29 北京林业大学 Preparation method and application of kaempferol imprinted microsphere based on nanometer titanium dioxide
CN105646805A (en) * 2016-03-26 2016-06-08 吉首大学 Nano TiO2 surface loaded Cu<2+>-nicotine-N-Nitrosodiethylamine composite imprinted material and application
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
CN109663581A (en) * 2018-12-03 2019-04-23 昆明理工大学 A method of cobalt (II) ion blotting composite membrane is prepared with N- pyrrolidinyl acrylamide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259229A (en) * 1979-05-16 1981-03-31 Nikitin Jury E Process for producing colored polymer
US20070191551A1 (en) * 2006-02-16 2007-08-16 Sungkyunkwan University Foundation For Corporate Collaboration Selective separation of heavy metal ion using metal ion imprinted polymer (MMIP)
CN104804134A (en) * 2014-01-26 2015-07-29 北京林业大学 Preparation method and application of isorhamnetin surface molecularly imprinted microsphere based on nanometer titanium dioxide
CN104804152A (en) * 2014-01-26 2015-07-29 北京林业大学 Preparation method and application of kaempferol imprinted microsphere based on nanometer titanium dioxide
CN105646805A (en) * 2016-03-26 2016-06-08 吉首大学 Nano TiO2 surface loaded Cu<2+>-nicotine-N-Nitrosodiethylamine composite imprinted material and application
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
CN109663581A (en) * 2018-12-03 2019-04-23 昆明理工大学 A method of cobalt (II) ion blotting composite membrane is prepared with N- pyrrolidinyl acrylamide

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