CN114984926A - Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer - Google Patents
Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer Download PDFInfo
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Abstract
A preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer relates to a preparation method of a lithium ion imprinted polymer. The invention aims to solve the problems that the existing method for recovering lithium is high in cost and complicated in steps, and the existing method for preparing the magnetic ion imprinted polymer is responsible for and easy to agglomerate, so that the adsorption capacity of lithium is reduced. The method comprises the following steps: firstly, preparation of Fe 3 O 4 /RGO; II, preparing Fe 3 O 4 @SiO 2 And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer. Compared with the existing lithium ion imprinted material, the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention has obvious agglomeration resistance, and the saturated adsorption capacity is remarkably improved. The high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention is used for lithiumThe adsorption rate of the ions can reach 99.9%. The invention can obtain the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer.
Description
Technical Field
The invention relates to a preparation method of a lithium ion imprinted polymer.
Background
The lithium ion battery has the advantages of long service life, high energy storage density, strong high-low temperature adaptability and the like, and is widely applied to new energy vehicles and various portable electronic products. The global consumption of lithium in 2021 reaches 90 ten thousand tons, and this figure tends to increase year by year. At present, the lithium source mainly comes from lithium ores, but the lithium ore resources are limited in China, but the salt lake resources are rich. Therefore, the extraction of lithium from salt lake water becomes a hot topic of resource conservation in recent years. The existing recovery technology is mainly electrochemical deposition and chemical deposition, but the recovery cost of the method is high and the steps are complicated. The ion imprinting technology is a new technology in the field of separation and purification, and has the characteristics of high specific efficiency and good selective separation effect, which are widely researched in recent years. The magnetic ion imprinting polymer combines the advantages of the ion imprinting technology and the magnetic separation technology, and has the characteristics of economy, high efficiency and easy realization of industrialization. However, the decrease of the adsorption capacity due to the agglomeration of the nanoparticle polymer and the complexity of the preparation process become major causes that hinder the further development of the technology.
Disclosure of Invention
The invention aims to solve the problems that the existing method for recovering lithium is high in cost and complicated in steps, and the existing method for preparing the magnetic ion imprinted polymer is responsible for and easy to agglomerate, so that the adsorption capacity of lithium is reduced, and provides the method for preparing the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer.
A preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is completed according to the following steps:
firstly, dissolving reduced graphene oxide in deionized water, and then adding FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 O, dropwise adding a NaOH solution under the conditions of water bath oscillation in a shaking table and nitrogen gas introduction into the solution, adjusting the pH value of the system, and finally carrying out water bath oscillation reaction in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; cleaning the reaction productWashing and drying to obtain Fe 3 O 4 /RGO；
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe 3 O 4 adding/RGO into absolute ethyl alcohol, uniformly stirring, then adding a mixed solution of deionized water/ammonia water, and carrying out water bath oscillation reaction to obtain a reaction product II;
secondly, firstly, washing the reaction product II by absolute ethyl alcohol, then washing the reaction product II by deionized water, and then washing the reaction product II by hydrochloric acid until no Li is detected by ICP-AES + Then, the reaction product II is washed by deionized water and finally dried in vacuum to obtain Fe 3 O 4 @SiO 2 And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
The invention adopts Reduced Graphene Oxide (RGO) as a framework material and takes Fe 3 O 4 Embedded on the surface thereof and combined with SiO 2 The modification method of the wrapped magnetic nanoparticles grafts 1-aza-12-crown 4-ether on the magnetic nanoparticles, and finally prepares the RGO-based magnetic lithium ion imprinted polymer with high agglomeration resistance through a one-step surface imprinted polymerization process, thereby having better application prospect.
The invention has the advantages that:
compared with the existing lithium ion imprinted material, the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention has obvious agglomeration resistance, and the saturated adsorption capacity is obviously improved;
the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the method has the advantages of simple preparation method, sensitive adsorption, energy conservation compared with other selective recovery means, and good circulation effect;
aiming at the complex environment in the pickle liquor of the waste lithium batteries, the magnetic material is introduced into the polymer, so that the magnetic separation and recovery after the polymer works are convenient;
fourthly, the adsorption rate of the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention to lithium ions can reach 99.9%.
The invention can obtain the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer.
Drawings
FIG. 1 is an SEM image of a high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1;
FIG. 2 is an SEM image of a high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1;
FIG. 3 is an SEM image of a highly agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting thereof. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer, which is specifically completed according to the following steps:
firstly, dissolving reduced graphene oxide in deionized water, and then adding FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 O, dropwise adding a NaOH solution under the conditions of water bath oscillation in a shaking table and nitrogen gas introduction into the solution, adjusting the pH value of the system, and finally carrying out water bath oscillation reaction in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; cleaning and drying the reaction product to obtain Fe 3 O 4 /RGO；
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe 3 O 4 adding/RGO into absolute ethyl alcohol, uniformly stirring, then adding a mixed solution of deionized water/ammonia water, and carrying out water bath oscillation reaction to obtain a reaction product II;
secondly, firstly, washing the reaction product II by absolute ethyl alcohol, then washing the reaction product II by deionized water, and then washing the reaction product II by hydrochloric acid until no Li is detected by ICP-AES + Then, the reaction product II is washed by deionized water and finally dried in vacuum to obtain Fe 3 O 4 @SiO 2 And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the mass ratio of the reduced graphene oxide to the deionized water in the first step is (0.33 g-3 g): 60 mL-200 mL; FeSO described in step one 4 ·7H 2 The mass ratio of the O to the deionized water is (1.2 g-3.6 g) to (60 mL-200 mL); FeCl as described in step one 3 ·6H 2 The ratio of the mass of the O to the volume of the deionized water is (2.33 g-6.99 g) to (60 mL-200 mL). Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the revolution of the rotary stirring of the shaking table is 60r/min to 120r/min, and the temperature of the water bath is 60 ℃ to 80 ℃; the reaction time in the first step is 1-2 h. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: adjusting the pH value of the system to 8-10 in the first step; the drying temperature in the first step is 30-50 ℃; the concentration of the NaOH solution in the first step is 1 mol/L. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: in the second step, the temperature of the water bath is 25-30 ℃, and the reaction time is 6-8 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the volume ratio of the mixed solution of the 1-aza-12-crown 4-ether, the 3-aminopropyl triethoxysilane, the tetraethoxysilane, the absolute ethyl alcohol and the deionized water/ammonia water in the second step is (0.3 mL-0.9 mL), (2 mL-6 mL), (8 mL-24 mL), (20 mL-60 mL) and (30 mL-90 mL). The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: anhydrous lithium chloride and Fe as described in step two 3 O 4 The mass ratio of/RGO is (1.29-3.87 g) to (1.33-4 g). The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the volume ratio of the mass of the anhydrous lithium chloride to the volume of the 1-aza-12-crown 4-ether in the second step is (1.29-3.8 g) to (0.3-0.9 mL). The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and the volume ratio of the deionized water to the ammonia water in the mixed solution of the deionized water and the ammonia water in the second step is 2:1, wherein the mass fraction of the ammonia water is 25-30%. The other steps are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: in the second step, the temperature of vacuum drying is 50-60 ℃; secondly, firstly, the reaction product II is cleaned for 3 to 5 times by using absolute ethyl alcohol, then the reaction product II is cleaned for 3 to 5 times by using deionized water, and then the reaction product II is cleaned by using hydrochloric acid with the mass fraction of 35 to 40 percent until the ICP-AES can not detect Li + Then, the reaction product II is washed by deionized water until the pH value is 7, and finally dried in vacuum to obtain Fe 3 O 4 @SiO 2 And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is characterized by comprising the following steps:
firstly, 1g of reduced graphene oxide is dissolved in 66.37mL of deionized water, and then 1.20g of FeSO is added 4 ·7H 2 O and 2.33g FeCl 3 ·6H 2 O, then 33.63mL of NaOH solution with the concentration of 1mol/L is dripped into the shaking table under the conditions of water bath oscillation at the temperature of 80 ℃ and nitrogen gas introduction into the solution, and finally the shaking table is used for water bath oscillation reaction for 1h under the protection of nitrogen gas atmosphere, and the reaction product I is obtained after the reaction is finished; washing the reaction product with deionized water for 6 times, and vacuum drying at 50 deg.C to obtain Fe 3 O 4 /RGO；
In the first step, the revolution of the rotary stirring of the shaking table is 60 r/min;
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 0.3mL of 1-aza-12-crown 4-ether, 1.29g of anhydrous lithium chloride, 2mL of 3-aminopropyltriethoxysilane, 8mL of ethyl orthosilicate and Fe obtained in the first step 3 O 4 adding/RGO into 20mL of absolute ethyl alcohol, uniformly stirring, then adding 30mL of deionized water/ammonia water mixed solution, and carrying out water bath oscillation reaction at 25 ℃ for 8 hours to obtain a reaction product II;
the volume ratio of the deionized water to the ammonia water in the mixed solution of the deionized water and the ammonia water in the second step is 2:1, wherein the mass fraction of the ammonia water is 25%;
secondly, firstly, washing the reaction product II for 5 times by using absolute ethyl alcohol, then washing the reaction product II for 3-5 times by using deionized water, and then washing the reaction product II by using hydrochloric acid with the mass fraction of 35% until the ICP-AES can not detect Li + The reaction product II was then washed with deionized water to a pH of 7 and finally dried under vacuum at 50 ℃ to give Fe 3 O 4 @SiO 2 And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
Example 2: a preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is characterized by comprising the following steps:
firstly, 0.33g of reduced graphene oxide is dissolved in 66.37mL of deionized water, and then 1.20g of FeSO is added 4 ·7H 2 O and 2.33g FeCl 3 ·6H 2 O, dripping 33.63mL of NaOH solution with the concentration of 1mol/L under the conditions of water bath oscillation at 80 ℃ in a shaking table and nitrogen gas introduction into the solution, and finally carrying out water bath oscillation reaction for 1h in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; washing the reaction product with deionized water for 6 times, and vacuum drying at 50 deg.C to obtain Fe 3 O 4 /RGO；
In the first step, the revolution of the rotary stirring of the shaking table is 60 r/min;
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 0.3mL of 1-aza-12-crown 4-ether, 1.29g of anhydrous lithium chloride, 2mL of 3-aminopropyltriethoxysilane, 8mL of ethyl orthosilicate and Fe obtained in the first step 3 O 4 adding/RGO into 20mL of absolute ethyl alcohol, uniformly stirring, then adding 30mL of deionized water/ammonia water mixed solution, and carrying out water bath oscillation reaction at 25 ℃ for 8 hours to obtain a reaction product II;
the volume ratio of the deionized water to the ammonia water in the mixed solution of the deionized water and the ammonia water in the second step is 2:1, wherein the mass fraction of the ammonia water is 28%;
secondly, firstly, washing the reaction product II for 5 times by using absolute ethyl alcohol, then washing the reaction product II for 3-5 times by using deionized water, and then washing the reaction product II by using hydrochloric acid with the mass fraction of 35% until the ICP-AES can not detect Li + Then the reaction product II was washed with deionized water to pH 7 and finally dried under vacuum at 50 ℃ to give Fe 3 O 4 @SiO 2 And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
Example 3: a preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is characterized by comprising the following steps:
firstly, 3g of reduced graphene oxide is dissolved in 66.37mL of deionized water, and then 1.20g F is addedeSO 4 ·7H 2 O and 2.33g FeCl 3 ·6H 2 O, dripping 33.63mL of NaOH solution with the concentration of 1mol/L under the conditions of water bath oscillation at 80 ℃ in a shaking table and nitrogen gas introduction into the solution, and finally carrying out water bath oscillation reaction for 1h in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; washing the reaction product with deionized water for 6 times, and vacuum drying at 50 deg.C to obtain Fe 3 O 4 /RGO；
In the first step, the revolution of the rotary stirring of the shaking table is 60 r/min;
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 0.3mL of 1-aza-12-crown 4-ether, 1.29g of anhydrous lithium chloride, 2mL of 3-aminopropyltriethoxysilane, 8mL of ethyl orthosilicate and Fe obtained in the first step 3 O 4 adding/RGO into 20mL of absolute ethyl alcohol, uniformly stirring, then adding 30mL of deionized water/ammonia water mixed solution, and carrying out water bath oscillation reaction at 25 ℃ for 8 hours to obtain a reaction product II;
the volume ratio of the deionized water to the ammonia water in the mixed solution of the deionized water and the ammonia water in the second step is 2:1, wherein the mass fraction of the ammonia water is 30%;
secondly, firstly, washing the reaction product II for 5 times by using absolute ethyl alcohol, then washing the reaction product II for 3-5 times by using deionized water, and then washing the reaction product II by using hydrochloric acid with the mass fraction of 35% until the ICP-AES can not detect Li + The reaction product II was then washed with deionized water to a pH of 7 and finally dried under vacuum at 50 ℃ to give Fe 3 O 4 @SiO 2 And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
FIG. 1 is an SEM image of a high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1;
FIG. 2 is an SEM image of a highly agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1;
FIG. 3 is an SEM image of the highly agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in example 1.
As can be seen from comparing fig. 1 to fig. 3, the polymer nanoparticles prepared in fig. 3 mostly have a single spherical shape, and have the best dispersibility; the polymer nanoparticles prepared in FIG. 1 begin to agglomerate, but a single spherical shape can still be seen; the agglomeration phenomenon of the polymer nanoparticles prepared in fig. 2 is most obvious, and the shape of a single sphere cannot be seen. Thus, RGO and Fe 3 O 4 When the mass ratio of (A) to (B) is 3:1, the prepared RGO-based magnetic lithium ion imprinted polymer has the best agglomeration resistance.
Application performance measurement:
0.2g of the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer prepared in examples 1 to 3 was added to 250mL of an aqueous solution containing lithium ions at a lithium ion concentration of 100mg/L, subjected to a shaking reaction, filtered, and the lithium ion concentration in the filtrate was measured, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, since RGO and Fe were added in example 2 3 O 4 Has the smallest mass ratio (1:3), obvious agglomeration phenomenon and the smallest specific surface area, thereby having the least lithium ion adsorption amount of 138.20mg/g, wherein RGO and Fe are adopted in example 3 3 O 4 The mass ratio (3:1) of (A) is the largest, the anti-agglomeration effect is good, the specific surface area is the largest, so that the adsorption amount is the best, and the adsorption amount is 256.43 mg/g. Example 1 addition of RGO and Fe 3 O 4 The mass ratio of (1:1) is moderate, the specific surface area and the adsorption quantity are also intermediate, and the adsorption quantity is 151.22 mg/g; therefore, the addition amount of RGO in a certain range is positively correlated with the adsorption amount, RGO has obvious contribution to the anti-agglomeration effect of the polymer, and RGO and Fe in the preparation process 3 O 4 The optimal mass ratio of (A) to (B) is 3: 1. Particularly, the adsorption capacity of the existing magnetic lithium ion imprinted polymer is approximately 130-150 mg/g, and compared with the existing magnetic lithium ion imprinted polymer, the adsorption capacity of the RGO-based magnetic lithium ion imprinted polymer with the high agglomeration resistance to lithium ions is greatly improved.
The RGO-based magnetic lithium ion imprinted polymer with high agglomeration resistance and the preparation method thereof proposed by the present invention have been described by way of examples, and it will be apparent to those skilled in the art that the present invention can be implemented by modifying or appropriately changing and combining the contents described herein without departing from the contents, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is characterized by comprising the following steps:
firstly, dissolving reduced graphene oxide in deionized water, and then adding FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 O, dropwise adding a NaOH solution under the conditions of water bath oscillation in a shaking table and nitrogen gas introduction into the solution, adjusting the pH value of the system, and finally carrying out water bath oscillation reaction in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; cleaning and drying the reaction product to obtain Fe 3 O 4 /RGO；
II, preparing Fe 3 O 4 @SiO 2 @IIP/RGO：
Firstly, 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe 3 O 4 adding/RGO into absolute ethyl alcohol, stirring uniformly, then adding a mixed solution of deionized water/ammonia water, and carrying out water bath oscillation reaction to obtain a reaction product II;
secondly, firstly, absolute ethyl alcohol is used for cleaning the reaction product II, then deionized water is used for cleaning the reaction product II, and hydrochloric acid is used for cleaning the reaction product II until ICP-AES can not detect Li + Then, the reaction product II is washed by deionized water and finally dried in vacuum to obtain Fe 3 O 4 @SiO 2 And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
2. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer according to claim 1, wherein the mass-to-volume ratio of the reduced graphene oxide to the deionized water in the step one is (0.33 g-3 g): (60 mL-200 mL); FeSO described in step one 4 ·7H 2 The mass ratio of the O to the deionized water is (1.2 g-3.6 g) to (60 mL-200 mL); FeCl as described in step one 3 ·6H 2 The mass ratio of O to the volume ratio of deionized water is (2.33 g-6.99 g) to (60 mL-200 mL).
3. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer according to claim 1, wherein the revolution number of the rotary table stirring in the first step is 60r/min to 120r/min, and the temperature of the water bath is 60 ℃ to 80 ℃; the reaction time in the first step is 1-2 h.
4. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the pH value of the system in the first step is adjusted to 8-10; the drying temperature in the first step is 30-50 ℃; the concentration of the NaOH solution in the first step is 1 mol/L.
5. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the temperature of the water bath in the second step is 25-30 ℃, and the reaction time is 6-8 h.
6. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of the mixed solution of 1-aza-12-crown 4-ether, 3-aminopropyltriethoxysilane, tetraethoxysilane, absolute ethanol and deionized water/ammonia water in the second step is (0.3 mL-0.9 mL): (2 mL-6 mL): (8 mL-24 mL): (20 mL-60 mL): (30 mL-90 mL).
7. According to claim1, the preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer is characterized in that anhydrous lithium chloride and Fe in the second step 3 O 4 The mass ratio of/RGO is (1.29-3.87 g) to (1.33-4 g).
8. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of the mass of the anhydrous lithium chloride to the volume of the 1-aza-12-crown 4-ether in the second step (1.29-3.8 g) to the volume of the 1-aza-12-crown 4-ether in the second step (0.3-0.9 mL).
9. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of deionized water to ammonia water in the deionized water/ammonia water mixed solution in the second step is 2:1, wherein the mass fraction of ammonia water is 25% -30%.
10. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the temperature of vacuum drying in the second step is 50-60 ℃; secondly, firstly, the reaction product II is cleaned for 3 to 5 times by using absolute ethyl alcohol, then the reaction product II is cleaned for 3 to 5 times by using deionized water, and then the reaction product II is cleaned by using hydrochloric acid with the mass fraction of 35 to 40 percent until the ICP-AES can not detect Li + Then, the reaction product II is washed by deionized water until the pH value is 7, and finally dried in vacuum to obtain Fe 3 O 4 @SiO 2 And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.
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| CN115400743A (en) * | 2022-11-01 | 2022-11-29 | 北京地之光企业管理有限公司 | Ion imprinting material for adsorbing lithium ions and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626611A (en) * | 2012-04-11 | 2012-08-08 | 哈尔滨工程大学 | Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance |
| CN102784615A (en) * | 2012-08-17 | 2012-11-21 | 中国科学院电工研究所 | Preparation method of magnetic copper ion imprinting silica gel material |
| CN105148876A (en) * | 2015-09-06 | 2015-12-16 | 江南大学 | Preparation method for surface molecular imprinting nano-composite material of magnetic graphene |
| CN105801782A (en) * | 2016-04-29 | 2016-07-27 | 江苏大学 | Preparation method of temperature-sensitive graphene oxide-based imprinted polymer and application thereof |
| IT201700026417A1 (en) * | 2017-03-09 | 2017-06-09 | Univ Ca Foscari Di Venezia | NEW MOLECULAR MOLD ELECTROCHEMICAL SENSORS FOR PERFLUOROOTTANSOLPHONATE AND ITS DERIVATIVES |
| CN108318421A (en) * | 2017-12-22 | 2018-07-24 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of magnetic graphene molecular engram Raman enhancing substrate and preparation method, application |
| KR20190010382A (en) * | 2017-07-20 | 2019-01-30 | 명지대학교 산학협력단 | Membrane for metal ion adsorption, method for manufacturing thereof and application thereof |
| CN110681367A (en) * | 2019-09-04 | 2020-01-14 | 太原理工大学 | Preparation method of nitrogen-doped carbon microsphere graphene composite aerogel lithium imprinted membrane for extracting lithium from acidic system |
| US20200083485A1 (en) * | 2013-03-15 | 2020-03-12 | Pixelligent Technologies, Llc | Advanced light extraction structure |
| WO2020093639A1 (en) * | 2018-11-08 | 2020-05-14 | 青岛大学 | Method for preparing phycoerythrin ratio fluorescence sensor based on magnetic molecular imprinted nucleus/shell polymer |
| CN112275267A (en) * | 2020-10-21 | 2021-01-29 | 中国农业科学院麻类研究所 | Magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin |
| CN113171689A (en) * | 2021-04-27 | 2021-07-27 | 东北电力大学 | Membrane preparation method combining nano particles with membrane surface microstructure construction |
| CN113402684A (en) * | 2021-07-02 | 2021-09-17 | 肇庆医学高等专科学校 | Preparation method of magnetic surface imprinting material and application of magnetic surface imprinting material in identification and resolution of amlodipine |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
-
2022
- 2022-05-11 CN CN202210508305.8A patent/CN114984926B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626611A (en) * | 2012-04-11 | 2012-08-08 | 哈尔滨工程大学 | Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance |
| CN102784615A (en) * | 2012-08-17 | 2012-11-21 | 中国科学院电工研究所 | Preparation method of magnetic copper ion imprinting silica gel material |
| US20200083485A1 (en) * | 2013-03-15 | 2020-03-12 | Pixelligent Technologies, Llc | Advanced light extraction structure |
| CN105148876A (en) * | 2015-09-06 | 2015-12-16 | 江南大学 | Preparation method for surface molecular imprinting nano-composite material of magnetic graphene |
| CN105801782A (en) * | 2016-04-29 | 2016-07-27 | 江苏大学 | Preparation method of temperature-sensitive graphene oxide-based imprinted polymer and application thereof |
| IT201700026417A1 (en) * | 2017-03-09 | 2017-06-09 | Univ Ca Foscari Di Venezia | NEW MOLECULAR MOLD ELECTROCHEMICAL SENSORS FOR PERFLUOROOTTANSOLPHONATE AND ITS DERIVATIVES |
| KR20190010382A (en) * | 2017-07-20 | 2019-01-30 | 명지대학교 산학협력단 | Membrane for metal ion adsorption, method for manufacturing thereof and application thereof |
| CN108318421A (en) * | 2017-12-22 | 2018-07-24 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of magnetic graphene molecular engram Raman enhancing substrate and preparation method, application |
| WO2020093639A1 (en) * | 2018-11-08 | 2020-05-14 | 青岛大学 | Method for preparing phycoerythrin ratio fluorescence sensor based on magnetic molecular imprinted nucleus/shell polymer |
| CN110681367A (en) * | 2019-09-04 | 2020-01-14 | 太原理工大学 | Preparation method of nitrogen-doped carbon microsphere graphene composite aerogel lithium imprinted membrane for extracting lithium from acidic system |
| CN112275267A (en) * | 2020-10-21 | 2021-01-29 | 中国农业科学院麻类研究所 | Magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
| CN113171689A (en) * | 2021-04-27 | 2021-07-27 | 东北电力大学 | Membrane preparation method combining nano particles with membrane surface microstructure construction |
| CN113402684A (en) * | 2021-07-02 | 2021-09-17 | 肇庆医学高等专科学校 | Preparation method of magnetic surface imprinting material and application of magnetic surface imprinting material in identification and resolution of amlodipine |
Non-Patent Citations (3)
| Title |
|---|
| XUBIAO LUO ET.AL: "Recovery of lithium from wastewater using development of Li ion-imprinted polymers", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| 梁琦;赵宏;刘伟峰;张二辉;闫光;杨永珍;刘旭光;: "锂离子印迹材料选择性提取锂的研究进展", 材料工程, no. 10 * |
| 费贵强;白浩;邵彦明;王海花;李璐璐;: "磁性表面分子印迹聚合物(Fe_3O_4@mSiO_2@MIP)的制备及四溴双酚A检测研究", 陕西科技大学学报, no. 02 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400743A (en) * | 2022-11-01 | 2022-11-29 | 北京地之光企业管理有限公司 | Ion imprinting material for adsorbing lithium ions and preparation method thereof |
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