CN106902654B - Preparation method and application of lithium ion imprinted polyether sulfone composite membrane - Google Patents
Preparation method and application of lithium ion imprinted polyether sulfone composite membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a lithium ion imprinted polyether sulfone composite membrane, belonging to the technical field of functional material preparation. The preparation method comprises the steps of taking a polyether sulfone membrane as a basement membrane material, taking lithium ions as a template, taking 12-crown-4-ether as a binding site, taking methacrylic acid as a functional monomer, taking ethylene glycol dimethacrylate as a cross-linking agent and taking azobisisobutyronitrile as an initiator, and combining a dopamine surface modification technology, a silicon dioxide nano-composite technology and an imprinting polymerization technology to prepare the lithium ion imprinting polyether sulfone composite membrane. The static adsorption experiment is used for researching the adsorption balance, adsorption kinetics and selective recognition performance of the prepared lithium ion imprinted polyether sulfone composite membrane; the selective permeation experiment is used for researching the permeation performance of the prepared lithium ion imprinting polyether sulfone composite membrane on target ions (lithium ions) and non-target ions (sodium ions and potassium ions). The lithium ion imprinted polyether sulfone composite membrane prepared by the method has higher specific adsorption capacity and identification and separation capacity for lithium ions.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a lithium ion imprinted polyether sulfone composite membrane for selectively identifying and separating lithium ions in a mixed system.
Background
Membrane Separation Technology (MST) is a separation technology that has attracted much attention in recent years, and particularly relates to a technology that separates a mixture of substances by blocking a part of the substances from passing through a membrane material when a mixture of molecules having different particle sizes passes through the membrane material on a molecular level. Compared with the traditional separation modes such as distillation, extraction and the like, the membrane separation process has the advantages of less loss of effective components, low energy consumption, no secondary pollution to separated substances, strong adaptability, simple process, convenient operation, easy automation and the like. However, for the separation process on the ion layer surface, the conventional microfiltration membrane, nanofiltration membrane, etc. lack single selectivity, thus limiting the wider application of the membrane separation technology.
Ion Imprinting (IIT) is a technology which is of great interest in recent years, and the emergence of IIT well solves the problem that membrane materials are not selective to ions. Under the condition of the existence of template ions, a coordination polymer coexisting with the template ions is formed on the surface of the membrane through the polymerization process between a functional monomer and a cross-linking agent, the template ions are eluted based on a physical or chemical method, imprinted sites matched with the template ions in space size and acting force are left on the surface of the membrane, and when mixed ions pass through the imprinted membrane, the imprinted sites can specifically adsorb target ions and simultaneously do not specifically adsorb non-template ions, so that the separation of single ions is realized. The Ion Imprinted Membrane (IIM) prepared by combining MST and IIT has the advantages of easiness in operation, low separation energy consumption, strong single selectivity and the like. In addition, compared with the traditional imprinted microspheres, the bulk imprinted polymers and the like, the IIM has the advantages of stable property, simple preparation process, wide application range, regular form and the like, and is a separation material with good application prospect. Currently, with the rapid development of MST, IIM has been widely used in many fields such as chemical industry, food, medicine, and the like.
Lithium element (lithonium) is an element with large abundance in nature, and is mainly applied to the fields of atomic reactor control, light alloy, battery preparation and the like. The lithium element is mainly distributed in mineral and natural salt lake brine, wherein 60 percent of lithium compounds are from the salt lake brine. Although it is currently about salt lake extractionThe separation of lithium has been widely studied with respect to methods such as solvent extraction, salting out, ion exchange, precipitation, and nanofiltration, but due to lithium ion (Li)+) With sodium ion (Na)+) And potassium ion (K)+) The properties of the lithium ion separation membrane are similar, and the ionic radii of the lithium ion separation membrane are similar, so that the lithium ion separation membrane can not realize the high-efficiency separation of lithium ions in salt lake brine at present. Researches show that the molecular structure of the 12-crown-4-ether has a special structure which can be matched with lithium ions in space, so that the molecular structure can be specifically combined with the lithium ions, and the adsorption separation material prepared based on the principle can realize a selective separation process of the lithium ions. In the application of the invention, the polyethersulfone is used as a basic membrane, and the lithium ion imprinting composite membrane material with high-efficiency selective recognition and separation capability on lithium ions is prepared by nano modification and ion imprinting technology.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion imprinting polyether sulfone composite membrane for selectively identifying and separating lithium ions in a mixed system.
The invention prepares the lithium ion imprinted polyether sulfone composite membrane with high-efficiency selective recognition and separation capability on lithium ions by taking a non-covalent imprinted system as a basis and combining a membrane separation technology, a dopamine surface polymerization technology, a nano composite modification technology and an ion imprinting technology, and applies the prepared membrane material to the separation process of the lithium ions in a mixed system.
The technical scheme of the invention is that polyether sulfone membranes (PSMs, the average pore diameter is 0.22 mu m, the diameter is 25mm) are taken as substrate membrane materials, the surface modification is carried out on the PSMs by utilizing a dopamine surface polymerization technology to obtain dopamine modified membranes dPSMs, and the silicon dioxide composite membranes SiO are prepared on the basis of a nano composite technology2@ dPSMs, advantageSurface modification of the composite membrane with gamma- (methacryloyloxy) propyltrimethoxysilane (KH-570) by lithium ion (Li)+) The Li-IIMs are prepared by taking 12-crown-4-ether as a binding site, methacrylic acid (MAA) as a functional monomer, Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent and Azobisisobutyronitrile (AIBN) as an initiator and initiating polymerization by utilizing a membrane surface functional monomer based on an imprinting technology.
A preparation method of a lithium ion imprinted polyether sulfone composite membrane initiated by a surface functional monomer prepolymerization system comprises the following specific steps:
step one, modifying the dopamine on the surface of a polyether sulfone membrane
Firstly, 0.1211g of Tris (hydroxymethyl) aminomethane hydrochloride (Tris) and 0.2g of dopamine hydrochloride (DA) are placed in 100mL of deionized water, the three solutions are uniformly mixed under the ultrasonic condition, the pH value of the mixed solution is adjusted to be 8.5, 3 polyether sulfone membrane PSMs are immersed in the mixed solution, the reaction is carried out for 3-9 hours under the oscillation at room temperature, the membrane obtained after the reaction is taken out, the membrane is immersed and cleaned with the deionized water for three times, 10 minutes each time, and the cleaned membrane is dried at room temperature to obtain the dopamine modified polyether sulfone membrane (dPSMs).
Step two, preparation of silicon dioxide nano composite film
First, 1mL of tetraethyl silicate (TEOS) was added to a mixed solution of 35mL of ethanol and water (ethanol: water: 30mL:5mL), the mixture was mixed uniformly under ultrasonic conditions, 3 sheets of the dopamine-modified polyethersulfone membrane dpmss obtained in step one were added to the mixed solution, and then the mixture was shaken at room temperature for 5 minutes, and 0.5mL of ammonia (NH) was added thereto3·H2O), continuing to perform oscillation reaction for 3-9 hours, taking out the membrane obtained after the reaction, respectively soaking and cleaning the membrane with ethanol and water for three times, 10 minutes each time, and airing at room temperature to obtain the silicon dioxide nano composite membrane (SiO)2@dPSMs)。
Step three, SiO2Surface modification of @ dPSMs
Firstly, 3 pieces of SiO obtained in the second step2@ dPSMs were added to a mixed solution of 100mL of ethanol and water (80 mL:20mL of ethanol: water), and nitrogen was introduced into the solution (N)2)5 minutes, add 3mL gamma- (methyl) under nitrogenIntroducing nitrogen into the solution for 10 minutes, sealing the solution by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting the solution in a 80 ℃ constant-temperature water bath oscillator for 12 to 20 hours, taking out the film obtained after the reaction, soaking and cleaning the film for 10 minutes each time by using ethanol and water respectively for three times, and airing the film at room temperature to obtain the modified silicon dioxide nano composite film (k-SiO)2@dPSMs)。
Step four, preparation of lithium ion imprinting polyether sulfone composite membrane
Firstly, 0.2mmol of lithium chloride (LiCl), 0.2mmol of 12-crown-4-ether (12C4) and 60mL of acetonitrile are uniformly mixed under the ultrasonic condition, and the mixed solution is stirred for 1 hour under the room temperature condition to ensure that lithium ions are fully combined with the 12-crown-4-ether; adding 3 sheets of k-SiO obtained in the third step into the mixed solution2Feeding nitrogen into the solution for 20 minutes after @ dPSMs, adding a certain amount of methacrylic acid (MAA), Ethylene Glycol Dimethacrylate (EGDMA) and Azobisisobutyronitrile (AIBN) into the mixed solution according to the proportion of 1:4:25 (millimole: milligram) under the condition of keeping nitrogen feeding, continuing to feed nitrogen for 5 minutes, sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting for 12-36 hours in a constant-temperature water bath oscillator at 60 ℃, taking out the film obtained after the reaction, respectively soaking and cleaning the film for three times by using ethanol and water, each time for 10 minutes, and airing at room temperature to obtain a imprinted polymeric film; and (3) placing 1 imprinted polymer membrane in 100mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out template elution treatment on the imprinted polymer membrane under room temperature oscillation, changing the eluent once every 6 hours, continuing the elution process for 3 days, and airing at room temperature to obtain the lithium ion imprinted polyether sulfone composite membrane (Li-IIMs).
The tris (hydroxymethyl) aminomethane hydrochloride in the above technical scheme functions as a buffer solution.
The dopamine hydrochloride in the technical scheme is used as a surface modification material.
The tetraethyl silicate in the technical scheme is used as a hydrolysis raw material.
The ammonia water in the technical scheme is used as a hydrolysis catalyst.
The gamma- (methacryloyloxy) propyl trimethoxy silane in the technical scheme is used as a silane coupling agent.
The lithium chloride in the technical scheme has the function of providing template ions.
The 12-crown-4-ether in the technical scheme has the function of providing a cavity for absorbing lithium ions.
The methacrylic acid in the technical scheme is used as a functional monomer.
The ethylene glycol dimethacrylate in the technical scheme is used as a cross-linking agent.
The azobisisobutyronitrile in the technical scheme has the function of an initiator.
The hydrochloric acid in the above technical scheme acts as an eluent.
The polyether sulfone membrane in the technical scheme is used as a base membrane material.
Testing of Material Properties
In order to form a contrast with the adsorption and separation performance of the lithium ion imprinted polyethersulfone composite membrane (Li-IIMs) prepared in the technical scheme, the preparation process of the non-imprinted membrane (Li-NIMs) is similar to that of the Li-IIMs while the Li-IIMs is prepared, and the other steps are the same as that of the Li-IIMs except that 12C4 is not added in the fourth preparation step.
(i) Static adsorption experiment and selective adsorption experiment
Adding certain mass of Li-IIMs or Li-NIMs into corresponding test solution, oscillating in constant temperature water bath at room temperature, examining the influence of the initial concentration of different adsorption solutions on the composite membrane, measuring the unadsorbed lithium ion concentration by using an inductively coupled plasma emission spectrometer (ICP) after adsorption is finished, and calculating the adsorption capacity (Q) according to the resulte，mg/g)：
Qe＝(C0-Ce)×V/m (1)
Wherein C is0(mg/L) and Ce(mg/L) concentrations of lithium ions in the solution before and after adsorption, m (g) masses of added Li-IIMs or Li-NIMs, and V (mL) test solutionThe volume of the liquid.
(ii) Selective permeability test
A self-made combined H-shaped glass infiltration device is characterized in that the middle of the H-shaped glass infiltration device is disconnected into two ground branch pipes, Li-IIMs or Li-NIMs are fixed between ground openings of two glass pools, a joint is sealed by using a degreasing adhesive tape and a waterproof adhesive tape to ensure that the device has no leakage, a mixed aqueous solution of lithium chloride, sodium chloride and potassium chloride with the same ion concentration is added into a sample pool on one side, equal volume of deionized water is added into a sample pool on the other side, one magneton is respectively placed into the two sample pools, stirring is carried out at room temperature, sampling is carried out at different time, the ion concentration penetrating through a imprinted composite membrane is measured by ICP, and the infiltration capacity is calculated according to the.
The invention has the advantages and technical effects that:
1. the method is characterized in that 12-crown-4-ether is fixed on the surface of a membrane material based on a surface imprinting polymerization technology, and a space cavity for selectively adsorbing lithium ions is provided by utilizing a cyclic molecular structure of the 12-crown-4-ether, so that the specific recognition and adsorption of the lithium ions are realized, and the lithium ions are separated from other ions through a permeation process;
2. according to the invention, imprinting polymerization is carried out on the surface, so that the problem that the adsorption effect is reduced due to too deep embedding of a recognition site is avoided, and the recognition efficiency of target ions (lithium ions) is greatly improved;
3. the lithium ion imprinted polyether sulfone composite membrane prepared by the invention has the advantages of high selectivity and obvious separation effect on lithium ions, and has the characteristics of high stability, strong reproducibility and repeated use.
Drawings
FIG. 1 is a schematic diagram of the preparation process of Li-IIMs and the mechanism of lithium ion adsorption.
FIGS. 2a and 2b are a bar graph of the static adsorption amount of Li-IIMs/Li-NIMs and a bar graph of the selective adsorption amount of Li-IIMs in examples 1 to 3, respectively.
FIGS. 3a to 3e show PSMs, dPSMs and SiO in example 2, respectively2@ dPSMs, modified SiO2Scanning electron micrographs of @ dPSMs and Li-IIMs.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Step one, modifying the dopamine on the surface of a polyether sulfone membrane
Firstly, 0.1211g of Tris (hydroxymethyl) aminomethane hydrochloride (Tris) and 0.2g of dopamine hydrochloride (DA) are placed in 100mL of deionized water, the three solutions are uniformly mixed under the ultrasonic condition, the pH value of the mixed solution is adjusted to be 8.5, 3 pieces of polyethersulfone membrane PSMs are immersed in the mixed solution, the reaction is carried out for 3 hours under the oscillation at room temperature, the membrane obtained after the reaction is taken out, the membrane obtained after the reaction is immersed and cleaned with the deionized water for three times, 10 minutes each time, and the cleaned membrane is dried at room temperature to obtain the dopamine modified polyethersulfone membrane (dPSMs).
Step two, preparation of silicon dioxide nano composite film
First, 1mL of tetraethyl silicate (TEOS) was added to a mixed solution of 35mL of ethanol and water (ethanol: water: 30mL:5mL), and the mixture was mixed uniformly under ultrasonic conditions, and after 3 sheets of the dopamine-modified polyethersulfone membrane dpmss obtained in step one were added to the mixed solution, the mixture was shaken at room temperature for 5 minutes, and 0.5mL of ammonia (NH) was added thereto3·H2O) continuously oscillating for 3 hours, taking out the membrane obtained after the reaction, respectively soaking and cleaning the membrane by using ethanol and water for three times, 10 minutes each time, and airing at room temperature to obtain the silicon dioxide nano composite membrane (SiO)2@dPSMs)。
Step three, SiO2Surface modification of @ dPSMs
Firstly, 3 pieces of SiO obtained in the second step2@ dPSMs were added to a mixed solution of 100mL of ethanol and water (80 mL:20mL of ethanol: water), and nitrogen was introduced into the solution (N)2) Adding 3mL of gamma- (methacryloyloxy) propyl trimethoxy silane (KH-570) in the presence of nitrogen for 5 minutes, continuously introducing nitrogen into the solution for 10 minutes, sealing the solution by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting the solution for 12 hours in a 80 ℃ constant-temperature water bath oscillator, taking out the film obtained after the reaction, respectively soaking and cleaning the film by using ethanol and water for 10 minutes each time, and drying the film at room temperature to obtain the modified silicon dioxide nano composite film (k-SiO) after drying the film at room temperature2@dPSMs)。
Step four, preparation of lithium ion imprinting polyether sulfone composite membrane
Firstly, 0.2mmol of lithium chloride (LiCl), 0.2mmol of 12-crown-4-ether (12C4) and 60mL of acetonitrile are uniformly mixed under the ultrasonic condition, and the mixed solution is stirred for 1 hour under the room temperature condition to ensure that lithium ions are fully combined with the 12-crown-4-ether; adding 3 sheets of k-SiO obtained in the third step into the mixed solution2Feeding nitrogen into the solution for 20 minutes after @ dPSMs, adding 0.5mmol of methacrylic acid (MAA), 2mmol of Ethylene Glycol Dimethacrylate (EGDMA) and 12.5mg of Azobisisobutyronitrile (AIBN) into the mixed solution under the condition of keeping nitrogen feeding, continuing feeding nitrogen for 5 minutes, sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting for 12 hours in a constant-temperature water bath oscillator at 60 ℃, taking out the film obtained after the reaction, respectively soaking and cleaning the film for three times by using ethanol and water, each time for 10 minutes, and airing the film at room temperature to obtain a imprinted polymeric film; and (3) placing 1 imprinted polymer membrane in 100mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out template elution treatment on the imprinted polymer membrane under room temperature oscillation, changing the eluent once every 6 hours, continuing the elution process for 3 days, and airing at room temperature to obtain the Li-IIMs-1 of the lithium ion imprinted polyether sulfone composite membrane.
Testing of Material Properties
(i) Static adsorption experiment and selective adsorption experiment
Respectively weighing 5 parts of Li-IIMs-1 and Li-NIMs-1, respectively putting the Li-IIMs-1 and the Li-NIMs-1 into 10 glass test tubes, respectively adding 10mL of lithium chloride aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L, respectively, oscillating the solution for 3 hours at room temperature, measuring the concentration of lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
The adsorption amounts of Li-IIMs-1 and Li-NIMs-1 are shown in FIG. 2(a), and the results show that the maximum saturated adsorption capacity of Li-IIMs-1 is 125.62mg/g, which is significantly higher than 75.48mg/g of Li-NIMs-1.
Weighing 5 parts of Li-IIMs-1, respectively putting the Li-IIMs-1 into 5 glass test tubes, respectively adding 10mL of mixed aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L containing lithium ions, sodium ions and potassium ions with the same concentration, shaking for 3 hours at room temperature, measuring the concentration of the lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
Li-IIMs-1 and Li-NIMs-1 to Li+、Na+、K+The adsorption amount of (b) is shown in FIG. 2(b), and the results show that the maximum saturated adsorption capacity of Li-IIMs-1 in competitive adsorption for lithium ions is 125.62mg/g, the maximum saturated adsorption capacity for sodium ions and potassium ions is 82.97mg/g and 67.41mg/g, respectively, and the selection factors are 1.51 and 1.86, respectively.
(ii) Selective permeability test
A self-made combined H-shaped glass infiltration device is characterized in that the middle of the device is disconnected into two ground branch pipes, Li-IIMs-1 or Li-NIMs-1 is fixed between ground openings of two glass pools, a joint is sealed by using a degreasing adhesive tape and a waterproof adhesive tape to ensure that the device has no leakage, a mixed aqueous solution of lithium chloride, sodium chloride and potassium chloride with the same ion concentration is added into a sample pool on one side, deionized water with the same volume is added into a sample pool on the other side, two magnetons are respectively placed into the two sample pools, the device is placed in a constant-temperature water bath and stirred under the room temperature condition, the ion concentration penetrating through a imprinted composite membrane is measured by ICP, and the infiltration capacity is calculated according to the ion concentration.
The Li-IIMs-1 selective permeation experiment result shows that in a mixed aqueous solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes respectively, the lithium ion concentrations in blank sample pools are respectively 0.1718, 0.2213, 0.2570, 0.2647, 0.2899, 0.3113, 0.3270, 0.3395, 0.3957 and 0.4174mg/L, the sodium ion concentrations are respectively 1.2578, 1.5850, 1.7910, 1.8431, 2.0751, 2.1759, 2.3610, 2.5804, 2.6842 and 2.8052mg/L, and the potassium ion concentrations are respectively 1.3142, 1.7896, 2.0843, 2.2674, 2.4718, 2.6081, 2.8755, 3.0195, 3.3537 and 3.5928 mg/L.
The Li-NIMs-1 selective permeation experiment result shows that in a mixed aqueous solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is respectively 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes, the lithium ion concentrations in blank sample pools are respectively 1.1513, 1.5264, 2.1225, 2.2493, 2.3054, 2.5854, 2.8252, 2.9437, 3.6175 and 3.9142mg/L, the sodium ion concentrations are respectively 1.1419, 1.4329, 2.1506, 2.2193, 2.4172, 2.5120, 2.9360, 3.2382, 3.4335 and 3.9641mg/L, and the potassium ion concentrations are respectively 1.1212, 0.6066, 2.2967, 2.2824, 2.4795, 2.5825, 2.8736, 3.1042, 3.5170 and 3.8027 mg/L.
The scanning electron microscope image of the membrane material in the example 1 is similar to that of the example 2, and as can be seen from the scanning electron microscope image in the fig. 3, compared with membrane materials obtained in other steps, a uniformly dispersed imprinting polymer layer with an irregular shape appears on the surface of the finally obtained Li-IIMs, which proves that the ion imprinting polymer layer is successfully synthesized on the surface of the membrane, and the result shows that the prepared Li-IIMs have the performances of specifically adsorbing template ions (lithium ions) and promoting permeation of non-template ions (sodium ions and potassium ions) by combining with excellent selective adsorption data of the Li-IIMs.
Example 2
Step one, modifying the dopamine on the surface of a polyether sulfone membrane
Firstly, 0.1211g of Tris (hydroxymethyl) aminomethane hydrochloride (Tris) and 0.2g of dopamine hydrochloride (DA) are placed in 100mL of deionized water, the three solutions are uniformly mixed under the ultrasonic condition, the pH value of the mixed solution is adjusted to be 8.5, 3 polyether sulfone membrane PSMs are immersed in the mixed solution, the reaction is carried out for 6 hours under the oscillation at room temperature, the membrane obtained after the reaction is taken out, the membrane obtained after the reaction is immersed and cleaned with the deionized water for three times, 10 minutes each time, and the cleaned membrane is dried at room temperature to obtain the dopamine modified polyether sulfone membrane (dPSMs).
Step two, preparation of silicon dioxide nano composite film
First, 1mL of tetraethyl silicate (TEOS) was added to a mixed solution of 35mL of ethanol and water (ethanol: water: 30mL:5mL), and the mixture was mixed uniformly under ultrasonic conditions, and after 3 sheets of the dopamine-modified polyethersulfone membrane dpmss obtained in step one were added to the mixed solution, the mixture was shaken at room temperature for 5 minutes, and 0.5mL of ammonia (NH) was added thereto3·H2O) continuously oscillating for 6 hours, taking out the membrane obtained after the reaction, respectively soaking and cleaning the membrane by using ethanol and water for three times, 10 minutes each time, and airing at room temperature to obtain the silicon dioxide nano composite membrane (SiO)2@dPSMs)。
Step three, SiO2Surface modification of @ dPSMs
Firstly, 3 pieces of SiO obtained in the second step2@ dPSMs were added to a mixed solution of 100mL of ethanol and water (80 mL:20mL of ethanol: water), and nitrogen was introduced into the solution (N)2) Adding 3mL of gamma- (methacryloyloxy) propyl trimethoxy silane (KH-570) in the presence of nitrogen for 5 minutes, continuously introducing nitrogen into the solution for 10 minutes, sealing the solution by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting the solution for 16 hours in a 80 ℃ constant-temperature water bath oscillator, taking out the film obtained after the reaction, respectively soaking and cleaning the film by using ethanol and water for 10 minutes each time, and drying the film at room temperature to obtain the modified silicon dioxide nano composite film (k-SiO) after the film is dried2@dPSMs)。
Step four, preparation of lithium ion imprinting polyether sulfone composite membrane
Firstly, 0.2mmol of lithium chloride (LiCl), 0.2mmol of 12-crown-4-ether (12C4) and 60mL of acetonitrile are uniformly mixed under the ultrasonic condition, and the mixed solution is stirred for 1 hour under the room temperature condition to ensure that lithium ions are fully combined with the 12-crown-4-ether; adding 3 sheets of k-SiO obtained in the third step into the mixed solution2@ dPSMs, introducing nitrogen into the solution for 20 minutes, adding 1mmol of methacrylic acid (MAA), 4mmol of Ethylene Glycol Dimethacrylate (EGDMA) and 25mg of Azobisisobutyronitrile (AIBN) into the mixed solution under the condition of keeping introducing nitrogen, continuing introducing nitrogen for 5 minutes, sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting for 24 hours in a constant-temperature water bath oscillator at 60 ℃, taking out the film obtained after the reaction, respectively soaking and cleaning the film for three times by using ethanol and water, each time for 10 minutes, and airing the film at room temperature to obtain a imprinted polymeric film; and (3) placing 1 imprinted polymer membrane in 100mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out template elution treatment on the imprinted polymer membrane under room temperature oscillation, changing the eluent once every 6 hours, continuing the elution process for 3 days, and airing at room temperature to obtain the Li-IIMs-2 of the lithium ion imprinted polyether sulfone composite membrane.
Testing of Material Properties
(i) Static adsorption experiment and selective adsorption experiment
Respectively weighing 5 parts of Li-IIMs-2 and Li-NIMs-2, respectively putting the Li-IIMs-2 and the Li-NIMs-2 into 10 glass test tubes, respectively adding 10mL of lithium chloride aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L, shaking for 3 hours at room temperature, measuring the concentration of lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
The adsorption amounts of Li-IIMs-2 and Li-NIMs-2 are shown in FIG. 2(a), and the results show that the maximum saturated adsorption capacity of Li-IIMs-2 is 172.43mg/g, which is significantly higher than 77.25mg/g of Li-NIMs-2.
Weighing 5 parts of Li-IIMs-2, respectively putting the Li-IIMs-2 into 5 glass test tubes, respectively adding 10mL of mixed aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L containing lithium ions, sodium ions and potassium ions with the same concentration, shaking for 3 hours at room temperature, measuring the concentration of the lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
Li-IIMs-2 and Li-NIMs-2 vs Li+、Na+、K+The adsorption amount of (A) is shown in FIG. 2(b), and the results show that the maximum saturated adsorption capacity of Li-IIMs-2 for lithium ions in competitive adsorption is 172.43mg/g, the maximum saturated adsorption capacity for sodium ions and potassium ions is 93.34mg/g and 83.30mg/g, respectively, and the selection factors are 1.85 and 2.07, respectively.
(ii) Selective permeability test
A self-made combined H-shaped glass infiltration device is characterized in that the middle of the H-shaped glass infiltration device is disconnected into two ground branch pipes, Li-IIMs-2 or Li-NIMs-2 is fixed between ground openings of two glass pools, a joint is sealed by using a degreasing adhesive tape and a waterproof adhesive tape to ensure that the device has no leakage, a mixed aqueous solution of lithium chloride, sodium chloride and potassium chloride with the same ion concentration is added into a sample pool on one side, deionized water with the same volume is added into a sample pool on the other side, one magneton is respectively placed into the two sample pools, the device is placed in a constant-temperature water bath and stirred under the room temperature condition, the ion concentration penetrating through a imprinted composite membrane is measured by ICP, and the infiltration capacity is calculated according to.
The Li-IIMs-2 selective permeation experiment result shows that in a mixed water solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes respectively, the lithium ion concentrations in blank sample pools are 0.1151, 0.1879, 0.2269, 0.2396, 0.2664, 0.2734, 0.2919, 0.3015, 0.3762 and 0.3967mg/L respectively, the sodium ion concentrations are 0.9780, 1.3673, 1.7344, 2.0630, 2.1904, 2.2748, 2.5237, 2.6719, 2.7395 and 2.8948mg/L respectively, and the potassium ion concentrations are 1.3023, 1.7745, 2.0163, 2.2169, 2.4066, 2.5250, 2.8525, 3.1170, 3.5364 and 3.8421mg/L respectively.
The Li-NIMs-2 selective permeation experiment result shows that in a mixed aqueous solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is respectively 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes, the lithium ion concentrations in blank sample pools are respectively 1.1845, 1.5592, 2.1649, 2.2705, 2.3498, 2.5807, 2.8934, 2.9471, 3.6910 and 3.9948mg/L, the sodium ion concentrations are respectively 1.0972, 1.3879, 1.8061, 2.1968, 2.2347, 2.2948, 2.8661, 3.2093, 3.7860 and 3.8795mg/L, and the potassium ion concentrations are respectively 1.2419, 1.7448, 2.2156, 2.3491, 2.4625, 2.5661, 2.8614, 3.1948, 3.5493 and 3.8834 mg/L.
As can be seen from the scanning electron microscope image in FIG. 3, compared with the membrane materials obtained in other steps, a layer of uniformly dispersed imprinting polymer layer with an irregular shape appears on the surface of the finally obtained Li-IIMs, which proves that the ion imprinting polymer layer is successfully synthesized on the surface of the membrane, and the result shows that the prepared Li-IIMs have the performances of specifically adsorbing template ions (lithium ions) and promoting permeation of non-template ions (sodium ions and potassium ions) by combining with excellent selective adsorption data of the Li-IIMs.
Example 3
Step one, modifying the dopamine on the surface of a polyether sulfone membrane
Firstly, 0.1211g of Tris (hydroxymethyl) aminomethane hydrochloride (Tris) and 0.2g of dopamine hydrochloride (DA) are placed in 100mL of deionized water, the three solutions are uniformly mixed under the ultrasonic condition, the pH value of the mixed solution is adjusted to be 8.5, 3 polyether sulfone membrane PSMs are immersed in the mixed solution, the reaction is carried out for 9 hours under the oscillation at room temperature, the membrane obtained after the reaction is taken out, the membrane obtained after the reaction is immersed and cleaned with the deionized water for three times, 10 minutes each time, and the cleaned membrane is dried at room temperature to obtain the dopamine modified polyether sulfone membrane (dPSMs).
Step two, preparation of silicon dioxide nano composite film
First, 1mL of tetraethyl silicate (TEOS) was added to a mixed solution of 35mL of ethanol and water (ethanol: water: 30mL:5mL), and the mixture was mixed uniformly under ultrasonic conditions, and after 3 sheets of the dopamine-modified polyethersulfone membrane dpmss obtained in step one were added to the mixed solution, the mixture was shaken at room temperature for 5 minutes, and 0.5mL of ammonia (NH) was added thereto3·H2O) continuously oscillating for 9 hours, taking out the membrane obtained after the reaction, respectively soaking and cleaning the membrane by using ethanol and water for three times, 10 minutes each time, and airing at room temperature to obtain the silicon dioxide nano composite membrane (SiO)2@dPSMs)。
Step three, SiO2Surface modification of @ dPSMs
Firstly, 3 pieces of SiO obtained in the second step2@ dPSMs were added to a mixed solution of 100mL of ethanol and water (80 mL:20mL of ethanol: water), and nitrogen was introduced into the solution (N)2) Adding 3mL of gamma- (methacryloyloxy) propyl trimethoxy silane (KH-570) in the presence of nitrogen for 5 minutes, continuously introducing nitrogen into the solution for 10 minutes, sealing the solution by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting the solution for 20 hours in a 80 ℃ constant-temperature water bath oscillator, taking out the film obtained after the reaction, respectively soaking and cleaning the film by using ethanol and water for 10 minutes each time, and drying the film at room temperature to obtain the modified silicon dioxide nano composite film (k-SiO) after the film is dried2@dPSMs)。
Step four, preparation of lithium ion imprinting polyether sulfone composite membrane
Firstly, 0.2mmol of lithium chloride (LiCl), 0.2mmol of 12-crown-4-ether (12C4) and 60mL of acetonitrile are uniformly mixed under the ultrasonic condition, and the mixed solution is stirred for 1 hour under the room temperature condition to ensure that lithium ions are fully combined with the 12-crown-4-ether; adding 3 sheets of k-SiO obtained in the third step into the mixed solution2@ dPSMs, then introducing nitrogen into the solution for 20 minutes, adding 2mmol of methacrylic acid (MAA), 8mmol of Ethylene Glycol Dimethacrylate (EGDMA) and 50mg of Azobisisobutyronitrile (AIBN) to the above mixed solution while keeping introducing nitrogen, continuing introducing nitrogen for 5 minutes, and then vacuum-evaporating the mixed solutionSealing the plug, the degreasing adhesive tape and the preservative film, reacting for 36 hours in a constant-temperature water bath oscillator at 60 ℃, taking out the film obtained after the reaction, respectively soaking and cleaning the film for 10 minutes each time for three times by using ethanol and water, and airing the film at room temperature to obtain the imprinted polymeric film; and (3) placing 1 imprinted polymer membrane in 100mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out template elution treatment on the imprinted polymer membrane under room temperature oscillation, changing the eluent once every 6 hours, continuing the elution process for 3 days, and airing at room temperature to obtain the Li-IIMs-3 of the lithium ion imprinted polyether sulfone composite membrane.
Testing of Material Properties
(i) Static adsorption experiment and selective adsorption experiment
Respectively weighing 5 parts of Li-IIMs-3 and Li-NIMs-3, respectively putting the Li-IIMs-3 and the Li-NIMs-3 into 10 glass test tubes, respectively adding 10mL of lithium chloride aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L, respectively, oscillating the solution for 3 hours at room temperature, measuring the concentration of lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
The adsorption amounts of Li-IIMs-3 and Li-NIMs-3 are shown in FIG. 2(a), and the results show that the maximum saturated adsorption capacity of Li-IIMs-3 is 148.59mg/g, which is significantly higher than 72.63mg/g of Li-NIMs-3.
Weighing 5 parts of Li-IIMs-3, respectively putting the Li-IIMs-3 into 5 glass test tubes, respectively adding 10mL of mixed aqueous solution with the concentration of 5, 10, 20, 50, 100 and 200mg/L containing lithium ions, sodium ions and potassium ions with the same concentration, shaking for 3 hours at room temperature, measuring the concentration of the lithium ions which are not adsorbed in the original solution through ICP after adsorption is finished, and calculating the adsorption capacity according to the result.
Li-IIMs-3 and Li-NIMs-3 vs Li+、Na+、K+The results show that the maximum saturated adsorption capacity of Li-IIMs-3 for lithium ions in competitive adsorption is 148.59mg/g, the maximum saturated adsorption capacity for sodium ions and potassium ions is 87.35mg/g and 74.68mg/g, respectively, and the selection factors are 1.70 and 1.98, respectively.
(ii) Selective permeability test
A self-made combined H-shaped glass infiltration device is characterized in that the middle of the H-shaped glass infiltration device is disconnected into two ground branch pipes, Li-IIMs-3 or Li-NIMs-3 is fixed between ground openings of two glass pools, a joint is sealed by using a degreasing adhesive tape and a waterproof adhesive tape to ensure that the device has no leakage, a mixed aqueous solution of lithium chloride, sodium chloride and potassium chloride with the same ion concentration is added into a sample pool on one side, deionized water with the same volume is added into a sample pool on the other side, one magneton is respectively placed into the two sample pools, the device is placed in a constant-temperature water bath and stirred under the room temperature condition, the ion concentration penetrating through a imprinted composite membrane is measured by ICP, and the infiltration capacity is calculated according to.
The Li-IIMs-3 selective permeation experiment result shows that in a mixed water solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes respectively, the lithium ion concentrations in blank sample pools are 0.1569, 0.2126, 0.2489, 0.2557, 0.2777, 0.2950, 0.3163, 0.3265, 0.3891 and 0.4057mg/L respectively, the sodium ion concentrations are 1.0175, 1.2649, 1.5498, 1.8310, 2.0563, 2.1544, 2.3653, 2.5740, 2.6931 and 2.7417mg/L respectively, and the potassium ion concentrations are 1.3137, 1.7864, 2.0273, 2.2287, 2.4185, 2.5360, 2.8641, 3.1287, 3.5474 and 3.8536mg/L respectively.
The Li-NIMs-3 selective permeation experiment result shows that in a mixed aqueous solution with initial lithium ion, sodium ion and potassium ion concentrations of 100mg/L, the sampling time is respectively 5, 10, 15, 30, 45, 60, 90, 120, 180 and 360 minutes, the lithium ion concentrations in blank sample pools are respectively 1.1785, 1.5424, 2.1782, 2.2405, 2.3945, 2.5449, 2.8412, 2.9177, 3.6052 and 3.9159mg/L, the sodium ion concentrations are respectively 1.1924, 1.4532, 2.1946, 2.2115, 2.4017, 2.5942, 2.9057, 3.2861, 3.4973 and 3.9527mg/L, and the potassium ion concentrations are respectively 1.1017, 1.6549, 2.2430, 2.2681, 2.4125, 2.5874, 2.8708, 3.1314, 3.5283 and 3.8913 mg/L.
The scanning electron microscope image of the membrane material in the embodiment 3 is similar to that of the embodiment 2, and as can be seen from the scanning electron microscope image in fig. 3, compared with membrane materials obtained in other steps, a uniformly dispersed imprinting polymer layer with an irregular shape appears on the surface of the finally obtained Li-IIMs, which proves that the ion imprinting polymer layer is successfully synthesized on the surface of the membrane, and the result shows that the prepared Li-IIMs have the performances of specifically adsorbing template ions (lithium ions) and promoting permeation of non-template ions (sodium ions and potassium ions) by combining with excellent selective adsorption data of the Li-IIMs.
The experimental data and the characterization results of the embodiment 1, the embodiment 2 and the embodiment 3 are combined, and the results show that the prepared Li-IIMs have higher specific adsorption on target ions (lithium ions) and have the performance of promoting permeation of non-target ions (sodium ions and potassium ions), namely the prepared Li-IIMs have the performance of efficiently identifying and separating lithium ions.
Claims (4)
1. A lithium ion imprinting polyether sulfone composite membrane is characterized in that: the polyether sulfone composite membrane is prepared by taking a polyether sulfone membrane as a base membrane material, carrying out surface dopamine modification on the polyether sulfone membrane based on a dopamine autopolymerization process, and establishing a secondary reaction platform on the surface of the polyether sulfone membrane; loading a silicon dioxide nano composite layer on the surface of the dopamine modified polyether sulfone membrane through a hydrolysis process to prepare a silicon dioxide nano composite membrane; modifying the membrane material by using gamma- (methacryloyloxy) propyl trimethoxy silane to prepare a modified silicon dioxide nano composite membrane; the lithium ion imprinted polyether sulfone composite membrane is prepared by taking lithium ions as a template, 12-crown-4-ether as a binding site, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent and azobisisobutyronitrile as an initiator based on a surface imprinting technology.
2. The preparation method of the lithium ion imprinted polyethersulfone composite membrane according to claim 1, characterized by comprising the following steps:
step one, modifying the dopamine on the surface of a polyether sulfone membrane
Placing 0.1211g of tris (hydroxymethyl) aminomethane hydrochloride and 0.2g of dopamine hydrochloride into 100mL of deionized water, uniformly mixing under an ultrasonic condition, adjusting the pH value of the mixed solution to 8.5, immersing 3 polyether sulfone membranes into the mixed solution, reacting for 3-9 hours under room temperature oscillation, taking out the membranes obtained after the reaction, immersing and cleaning the membranes for three times each time for 10 minutes by using the deionized water, and drying the cleaned membranes at room temperature to obtain the dopamine modified polyether sulfone membranes;
step two, preparation of silicon dioxide nano composite film
Adding 1mL of tetraethyl silicate into 35mL of mixed solution of ethanol and water, wherein the ethanol is 30mL:5mL, uniformly mixing under an ultrasonic condition, adding 3 dopamine-modified polyethersulfone membranes obtained in the first step into the mixed solution, oscillating for 5 minutes at room temperature, adding 0.5mL of ammonia water, continuing oscillating for 3-9 hours, taking out the membranes obtained after reaction, respectively soaking and cleaning the membranes with ethanol and water for three times, each time for 10 minutes, and airing at room temperature to obtain a silicon dioxide nano composite membrane;
step three, surface modification of silicon dioxide nano composite membrane
Adding 3 silicon dioxide nano composite films obtained in the second step into 100mL of mixed solution of ethanol and water, wherein the ethanol is 80mL of water and 20mL of water, introducing nitrogen into the solution for 5 minutes, adding 3mL of gamma- (methacryloyloxy) propyl trimethoxy silane under the protection of nitrogen, continuously introducing nitrogen into the solution for 10 minutes, sealing the solution by using a vacuum plug, a degreasing tape and a preservative film, reacting in a constant-temperature water bath oscillator at 80 ℃ for 12-20 hours, taking out the films obtained after the reaction, soaking and cleaning the films by using ethanol and water respectively for three times, each time for 10 minutes, and airing at room temperature to obtain a modified silicon dioxide nano composite film;
step four, preparation of lithium ion imprinting polyether sulfone composite membrane
Uniformly mixing 0.2mmol of lithium chloride, 0.2mmol of 12-crown-4-ether and 60mL of acetonitrile under an ultrasonic condition, and stirring the mixed solution at room temperature for 1 hour to fully combine lithium ions with the 12-crown-4-ether; adding 3 silicon dioxide nano composite films obtained in the third step into the mixed solution, introducing nitrogen into the mixed solution for 20 minutes, adding a certain amount of methacrylic acid, ethylene glycol dimethacrylate and azobisisobutyronitrile into the mixed solution according to the proportion of 1mmol to 4mmol to 25mg under the condition of keeping introducing nitrogen, continuously introducing nitrogen for 5 minutes, sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film, reacting in a constant-temperature water bath oscillator at 60 ℃ for 12-36 hours, taking out the film obtained after the reaction, soaking and cleaning the film respectively with ethanol and water for three times, each time for 10 minutes, and airing at room temperature to obtain an imprinted polymeric film; and (3) placing 1 imprinted polymer membrane in 100mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out template elution treatment on the imprinted polymer membrane under room temperature oscillation, changing the eluent once every 6 hours, continuing the elution process for 3 days, and airing at room temperature to obtain the lithium ion imprinted polyether sulfone composite membrane.
3. The lithium ion imprinted polyethersulfone composite membrane synthesized by the method for preparing the lithium ion imprinted polyethersulfone composite membrane according to claim 2.
4. The lithium ion imprinted polyethersulfone composite membrane of claim 3, wherein: the method is used for the selective adsorption and separation process of lithium ions in the mixed aqueous solution of the lithium ions, sodium ions and potassium ions.
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