CN117089020B - Based on nanometer TiO2Preparation method of Co (II) ion imprinting adsorption material - Google Patents
Based on nanometer TiO2Preparation method of Co (II) ion imprinting adsorption material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 88
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 cobalt ion compound Chemical class 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised 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
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
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Abstract
The invention discloses a preparation method of a Co (II) ion imprinting adsorption material based on nano TiO 2, and belongs to the technical field of adsorption separation of surface ion imprinting materials. 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 a ligand, alpha-methacrylic acid is used as a functional monomer, nano TiO 2 is used as a carrier, ethylene glycol dimethacrylate is used as a cross-linking agent, and azobisisobutyronitrile is used as an initiator; co (II) ion imprinted polymer was synthesized by thermal initiation surface imprinting technique at 60℃for 12 h. 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
Technical Field
The invention relates to a preparation method of a Co (II) ion imprinting adsorption material based on nano TiO 2, and belongs to the technical field of adsorption separation of surface ion imprinting materials.
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 desirable to have better entry of the template ions into the print cavity by controlling the template ions at the surface of the material to obtain more efficient recognition sites. 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 2O3、TiO2, carbon nanotubes, cdS, znS quantum dots, etc.). In addition, the nano TiO 2 as a novel inorganic material has many excellent performances such as innocuity, low cost, light stability, stable chemical property, high efficiency of photocatalysis effect and the like. Therefore, we selected TiO 2 nanoparticles as support matrix for the study.
Disclosure of Invention
The invention provides a preparation method of a Co (II) ion imprinting adsorption material based on nano TiO 2, which 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) The cobalt ion compound CoCl 2·6H2 O is dissolved in the pore-forming solvent according to the proportion of 0.005mmol/mL, and the 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 carrier nano TiO 2 according to the proportion of 1.25mg/mL, adding cross-linking agent glycol dimethacrylate according to the proportion of (0.05-0.25) mmol/mL, adding initiator azo-diisobutyronitrile according to the proportion of 1mg/mL, performing ultrasonic treatment for 10min to form a uniform solution, introducing N 2 min to remove oxygen in the solution, and polymerizing at 60 ℃ for 12h 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 preparation method of the Co (II) ion imprinting adsorption material based on the nano TiO 2 is relatively simple, and the required reagent and instrument equipment are relatively conventional, easy to operate and low in cost.
(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
The preparation method of the Co (II) ion imprinting adsorption material based on nano TiO 2 comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl 2·6H2 O was added to 20mL of methanol/water in a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added to react for 1h.
(2) 0.40Mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) 20.00Mg of carrier nano TiO 2, 1.00mmol of cross-linking agent ethylene glycol dimethacrylate and 20.00mg of initiator azo-bis-isobutyronitrile are added, then ultrasonic treatment is carried out for 10min to form a uniform solution, and N 2 min is introduced to remove oxygen in the solution. 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
The preparation method of the Co (II) ion imprinting adsorption material based on nano TiO 2 comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl 2·6H2 O was added to 20mL of methanol/water in a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added to react 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 ethylene glycol dimethacrylate and 20.00mg of initiator azo-bis-isobutyronitrile, performing ultrasonic treatment for 10min to form a uniform solution, and introducing N 2 min to remove oxygen in the solution; 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
The preparation method of the Co (II) ion imprinting adsorption material based on nano TiO 2 comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl 2·6H2 O was added to 20mL of methanol/water in a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added to react for 1h.
(2) 0.40Mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) 20.00Mg of carrier nano TiO 2, 3.00mmol of cross-linking agent ethylene glycol dimethacrylate and 20.00mg of initiator azodiisobutyronitrile are added, then ultrasonic treatment is carried out for 10min to form a uniform solution, and N 2 min is introduced to remove oxygen in the solution. 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
The preparation method of the Co (II) ion imprinting adsorbing material based on nano TiO 2 comprises the following specific steps of;
(1) 0.10mmol of cobalt ion compound CoCl 2·6H2 O was added to 20mL of methanol/water in a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added to react for 1h.
(2) 0.40Mmol of the functional monomer alpha-methacrylic acid was added and the mixture was shaken at 25℃for 2h.
(3) 20.00Mg of carrier nano TiO 2, 4.00mmol of cross-linking agent ethylene glycol dimethacrylate and 20.00mg of initiator azodiisobutyronitrile are added, then ultrasonic treatment is carried out for 10min to form a uniform solution, and N 2 min is introduced to remove oxygen in the solution. 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
The preparation method of the Co (II) ion imprinting adsorption material based on nano TiO 2 comprises the following specific steps:
(1) 0.10mmol of cobalt ion compound CoCl 2·6H2 O was added to 20mL of methanol/water in a volume ratio of 1:1, and 0.30mmol of ligand bis (2, 4-trimethylpentyl) phosphinic acid was added to react 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 ethylene glycol dimethacrylate and 20.00mg of initiator azodiisobutyronitrile, performing ultrasonic treatment for 10min to form a uniform solution, and introducing N 2 min to remove oxygen in the solution; 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 (5)
1. The preparation method of the Co (II) ion imprinting adsorption material based on the nano TiO 2 is characterized by comprising the following steps of:
(1) Dissolving cobalt ion compound CoCl 2•6H2 O in a pore-forming solvent according to the proportion of 0.005mmol/mL, and adding ligand bis (2, 4-trimethylpentyl) phosphinic acid according to the proportion of 0.015mmol/mL for reaction;
(2) Adding a functional monomer alpha-methacrylic acid according to the proportion of 0.02mmol/mL for reaction;
(3) Adding carrier nano TiO 2 according to the proportion of 1.25mg/mL, adding cross-linking agent ethylene glycol dimethacrylate according to the proportion of 0.05-0.25mmol/mL, adding initiator azo-diisobutyronitrile according to the proportion of 1mg/mL, uniformly mixing, introducing N 2 min to remove oxygen in the solution, and obtaining Co (II) ion imprinted polymer after the reaction is completed;
(4) Filtering the polymer, and removing Co (II) ions in the polymer by using 0.2mol/L EDTA to obtain a Co (II) ion imprinted polymer which is matched with the shape and the size of the template ions and has a three-dimensional cavity;
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 mol ratio of Co (II) ions, ligand, functional monomer and crosslinking agent is 1:3:4 (10-50).
2. The method for preparing the Co (II) ion imprinting adsorbing material based on nano TiO 2, which is characterized in that: the reaction time in step (1) was 1h.
3. The method for preparing the Co (II) ion imprinting adsorbing material based on nano TiO 2, which is characterized in that: the reaction conditions in step (2) were shaking at 25℃for 2h.
4. The method for preparing the Co (II) ion imprinting adsorbing material based on nano TiO 2, which is characterized in that: the conditions for uniform mixing in the step (3) are as follows: and (5) carrying out ultrasonic treatment for 10min.
5. The method for preparing the Co (II) ion imprinting adsorbing material based on nano TiO 2, which is characterized in that: the reaction condition in the step (3) is that the polymerization is carried out for 12 hours at 60 ℃.
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| 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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