CN112705173B - Functionalized UIO-66-NH2Composite membrane, preparation method thereof and application thereof in gallium adsorption - Google Patents

Functionalized UIO-66-NH2Composite membrane, preparation method thereof and application thereof in gallium adsorption Download PDF

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CN112705173B
CN112705173B CN202011479718.5A CN202011479718A CN112705173B CN 112705173 B CN112705173 B CN 112705173B CN 202011479718 A CN202011479718 A CN 202011479718A CN 112705173 B CN112705173 B CN 112705173B
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gallium
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娄振宁
赵雯艳
张蒙蒙
崔俊硕
单炜军
于海彪
王月娇
熊英
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Liaoning University
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Abstract

The invention relates to a functionalized UIO-66-NH2Preparation of a composite membrane and research application of the composite membrane to the field of gallium adsorption, belonging to the technical field of adsorbents. The technical scheme is as follows: selecting 3,4, 5-trihydroxy benzaldehyde modified UIO-66-NH with abundant hydroxyl2Then the functional UiO-66-NH is prepared by blending the functional UiO-66-NH with polyurethane with good flexibility and stability and electrostatic spinning2A composite membrane. The invention improves the defects of difficult liquid phase separation and poor cycle performance of the powdery metal organic framework composite material, improves the recovery efficiency of gallium ions and enhances the cycle performance. The maximum adsorption amount of the TPU/0.1THB/U6N-1.5 to Ga (III) is 96.18mg g at the optimum pH of 10, the equilibrium time of 8h, the temperature of 25 DEG C‑1Therefore, the method has strong practical applicability.

Description

Functionalized UIO-66-NH2Composite membrane, preparation method thereof and application thereof in gallium adsorption
Technical Field
The invention relates to the technical field of effective recovery of gallium and preparation of green film adsorbing materials, in particular to functionalized UIO-66-NH2A composite membrane, a preparation method thereof and application thereof in gallium adsorption.
Background
Gallium (Ga), a rare element located in the third main group of the fourth period, is present in low concentration in the earth's crust and exists mostly in the form of associated minerals, making extraction and separation of gallium ions difficult.
At present, methods for separating and pre-enriching gallium are mainly divided into extraction methods, precipitation methods, bioleaching methods, neutralization methods, complexation methods and ion exchange methods, however, most of the methods need to consume expensive chemical reagents, and can cause secondary pollution and environmental pollution, and especially, the method has poor effect in the case of treating low-concentration gallium solution. In contrast, the adsorption method is considered to be an environment-friendly and efficient metal ion recovery method due to the advantages of easy availability, low cost, no toxicity, recycling, abundant natural sources and the like. In choosing a suitable adsorbent material, two aspects are of concern: firstly, the stability of the adsorption material is improved; the second is the high affinity between the functionalized species and the metallic element. From the chemical viewpoint, gallium can form a stable complex with an oxygen-containing group such as a hydroxyl group or a carboxyl group. In recent years, various rare earth materials such as silicon-based materials, chitosan, activated carbon, carbon nanotubes, metal oxides, ion imprinting, and the like have been applied to the recovery of gallium elements.
The global interest in green and coal-free technologies is increased, the market value of gallium is obviously improved, and the gallium becomes an important raw material for further development of economy and industry in China. Gallium is a non-renewable resource, and continued intensive mining and lack of effective resource recovery strategies can result in significant gallium loss with wastewater. If the secondary resources lack an effective recovery means, the secondary resources not only cause harm to human health, but also cause environmental pollution. Therefore, it is important to develop a green process for recovering gallium from mining wastewater or municipal sewage.
MOFs materials are gradually regarded as important adsorption matrixes in the field of liquid phase separation due to the characteristics of large specific surface area, good water stability and the like. UIO-66-NH2Although the stability is good, UIO-66-NH2Lacking active sites for adsorption of gallium. Modification of the surface with 3,4, 5-Trihydroxybenzaldehyde (THB) introduces more hydroxyl groups to raise UIO-66-NH2The adsorption capacity of the material. In order to improve the defects that the powdered MOFs materials are easy to lose and difficult to recover in the adsorption process, the materials are selected to have acid and alkali resistance, high temperature resistance and good flexibilityAs a matrix material for electrospinning. UIO-66-NH functionalizing THB2And doping with polyurethane, and preparing the functionalized metal organic framework composite membrane by adopting electrostatic spinning.
The advantages of the adsorption method are more obvious compared with other recovery methods through some examples, so that the adsorption method is mainly adopted in the invention when the metal ions in the water are recovered. However, in practical applications, the adsorption method has the disadvantages of small adsorption quantity, poor selectivity, low adsorption rate and the like, so that a new material or method is urgently needed to solve the problems.
Disclosure of Invention
In order to improve the defects of difficult recovery and poor cycle performance of the powdery metal organic framework composite material in liquid phase separation, the invention uses 1,3, 5-trihydroxy benzaldehyde to UIO-66-NH2Post-synthesis modification is carried out to introduce rich hydroxyl groups, and then the functional metal organic framework composite membrane TPU/0.1THB/U6N-1.5 with acid resistance, durability and high flux is prepared by electrostatic spinning through compounding with polyurethane. TPU/0.1THB/U6N-1.5 can still reach about 90 percent of adsorption rate after 5 times of circulating elution, and can selectively adsorb gallium ions in a six-element mixed ion system, which shows that functionalized UIO-66-NH2The composite membrane has great potential in the aspect of recovering gallium ions in the aqueous solution, and the stability of the composite membrane in practical cyclic application is also greatly improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
functionalized UIO-66-NH2Composite membrane prepared from UIO-66-NH2The method is characterized in that the method is used as a matrix material, the surface of the matrix material is modified by 3,4, 5-Trihydroxybenzaldehyde (THB) to introduce more hydroxyl groups, polyurethane (TPU) is selected as the matrix material of electrostatic spinning, and the functionalized metal organic framework composite membrane is prepared by adopting the electrostatic spinning.
Preferably, the above-mentioned functionalized UIO-66-NH2The preparation method of the composite membrane comprises the following steps:
1) sequentially adding UiO-66-NH2(U6N) and 3,4, 5-Trihydroxybenzaldehyde (THB) into a three-necked flask, followed by addition of anhydrous ethanol and heating at 333-Reacting for 22-27h, washing for several times, and drying for 9-15h under 343-363K to obtain THB functionalized U6N;
2) polyurethane particles (TPU) are mixed with a mixed solution of Dimethylformamide (DMF) and Tetrahydrofuran (THF) and stirred thoroughly for 5-8h at 313-333K, followed by functionalization of UiO-66-NH2Adding the material into the suspension, stirring for 1-3h under the condition of 313-333K, then carrying out ultrasonic treatment for 10-15h at room temperature and stirring for 3-5h at room temperature, and carrying out electrostatic spinning on the obtained product to obtain the functionalized UiO-66-NH2A composite membrane.
Preferably, the above preparation method, the UiO-66-NH2The preparation method comprises the following steps: dissolving zirconium tetrachloride and ligand 2-amino terephthalic acid in a mixed solution of Dimethylformamide (DMF) and concentrated hydrochloric acid, fully stirring for 2-5h at room temperature, transferring to a polytetrafluoroethylene reaction kettle, reacting for 22-27h at 383-2。
Preferably, in the above preparation method, the volume ratio of concentrated hydrochloric acid to dimethylformamide is 1 to (13-15) in the mixed solution.
Preferably, in the above preparation method, step 1), the mass ratio of UiO-66-NH 23,4, 5-trihydroxy benzaldehyde is 1 to (0.1-1).
Preferably, in the above preparation method, step 2), the weight ratio of the polyurethane particles: functionalized UiO-66-NH 21 to (0.5-1.3).
Preferably, in the above preparation method, the conditions for performing electrostatic spinning are as follows: spinning at 25-30 deg.C, humidity of 75-80%, and injection speed of 10-12 μ L/min, and collecting the membrane on tinfoil paper or filter paper.
Preferably, the above-mentioned functionalized UIO-66-NH2The application of the composite membrane in gallium adsorption comprises the following steps: weighing the above functionalized UIO-66-NH2Mixing the composite membrane 20-25mg with gallium solutions with different acidity, vibrating, balancing, measuring the concentration of gallium ions in the adsorbed solution, and eluting with an eluent.
Preferably, in the above application, the pH of the gallium mixed solution is 3 or 10.
Preferably, in the above application, the eluent is HCl, and the HCl concentration is more than 1mol L-1。
The invention has the beneficial effects that:
(1) in the preparation method of the composite membrane, the preparation method is simple, the used raw materials are low in cost, and the composite membrane can be produced in large scale and is suitable for being applied to subsequent industrial production.
(2) The functionalized UIO-66-NH obtained by the invention2The composite membrane is simple in liquid phase separation, the cycle performance is improved, the adsorption capacity is large, the water flux is high, and the stability is good.
Drawings
FIG. 1 schematic diagram of the synthesis of TPU/0.1 THB/U6N-1.5.
In FIG. 2, A is the SEM picture of TPU, B is the SEM picture of TPU/0.1THB/U6N-0.75, C is the SEM picture of TPU/0.1THB/U6N-1.25, E and F are the SEM pictures of TPU/0.1THB/U6N-1.5, and D is the SEM picture of TPU/0.1 THB/U6N-2.0; panel a is the contact angle of TPU, b is the contact angle of TPU/0.1THB/U6N-1.5, and c is a picture of TPU/0.1 THB/U6N-1.5.
FIG. 3 the infrared spectra of TPU, TPU/0.1THB/U6N-1.5 and 0.1 THB/U6N.
FIG. 4 Effect of TPU/0.1THB/U6N-1.5 on gallium adsorption Performance in solutions of different acidity.
FIG. 5 shows the effect of U6N and xTHB/U6N on Ga (III) adsorption at different pH values.
FIG. 6 shows the adsorption isotherm of TPU/0.1THB/U6N-1.5 for gallium.
FIG. 7 Effect of initial gallium ion concentration on composite membrane Water flux (A) and on Ga (III) adsorption Performance (B).
FIG. 8 influence of temperature on composite membrane water flux (A) and on adsorption performance (B) of Ga (III).
FIG. 9 Effect of time on composite membrane Water flux (A) and on adsorption Performance (B) of Ga (III).
FIG. 10 the cycle performance of TPU/0.1 THB/U6N-1.5.
Detailed Description
In order that those skilled in the art may more fully understand the present invention, the invention will be described in more detail by way of the following non-limiting examples or comparative examples, which are not to be construed as limiting the invention in any way.
Example 1 functionalized UIO-66-NH2Composite membrane (TPU/0.1THB/U6N-1.5)
(one) UIO-66-NH2Preparation of (2)
Zirconium tetrachloride (0.250g,1.08mol) and ligand 2-aminoterephthalic acid (0.268g,1.5mol) were dissolved in a mixed solution of 30ml of dimethylformamide and 2ml of concentrated hydrochloric acid, and sufficiently stirred at room temperature for 3 hours. The solution was then transferred to a teflon reaction kettle and reacted at 393K for 24 h. The resultant was washed several times by centrifugation with DMF and absolute ethanol and dried under vacuum at 353K for 12 h.
Preparation of (II) THB functionalized U6N (0.1THB/U6N) material
0.5g of UiO-66-NH is weighed2(U6N) and 0.1g of 3,4, 5-Trihydroxybenzaldehyde (THB) to a 50mL three-necked flask. Subsequently, 25mL of absolute ethanol was added and reacted at 343K for 24h, and then the resulting product was washed several times with absolute ethanol and distilled water and after drying at 343K for 12h, the final product was obtained and named 0.1 THB/U6N.
(III) functionalized UIO-66-NH2Preparation of composite film (TPU/0.1THB/U6N-1.5)
1.5g of polyurethane particles are weighed out and mixed with a mixed solution of 5mL of dimethylformamide and 5mL of tetrahydrofuran and stirred thoroughly at 323K for 6 h. 1.5g of 0.1THB/U6N were then added to the suspension and stirred at 323K for 1h, followed by sonication for 12h at room temperature and stirring for 3h at room temperature. Performing electrostatic spinning on the obtained product to obtain functionalized UiO-66-NH2The composite membrane is named as TPU/0.1THB/U6N-1.5, and the synthetic route is shown in figure 1.
Example 2 functionalized UIO-66-NH2Composite membrane (TPU/0.1THB/U6N-0.75)
The steps (A) and (B) are the same as those (A) and (B) in example 1
(III) functionalized UIO-66-NH2Preparation of composite film (TPU/0.1THB/U6N-0.75)
1.5g of polyurethane particles were weighed and mixed with a mixed solution of 5mL of dimethylformamide and 5mL of tetrahydrofuranThe mixtures were stirred well at 323K for 6 h. 0.75g of 0.1THB/U6N was subsequently added to the suspension and stirred at 323K for 1h, followed by 12h of ultrasound at room temperature and 3h of stirring at room temperature. Performing electrostatic spinning on the obtained product to obtain functional UiO-66-NH2The composite membrane is named as TPU/0.1 THB/U6N-0.75.
Example 3 functionalized UIO-66-NH2Composite membrane (TPU/0.1THB/U6N-1.25)
The steps (A) and (B) are the same as those (A) and (B) in example 1
(III) functionalized UIO-66-NH2Preparation of composite film (TPU/0.1THB/U6N-1.25)
1.5g of polyurethane particles are weighed out and mixed with a mixed solution of 5mL of dimethylformamide and 5mL of tetrahydrofuran and stirred thoroughly at 323K for 6 h. 1.25g of 0.1THB/U6N were then added to the suspension and stirred at 323K for 1h, followed by 12h sonication at room temperature and 3h stirring at room temperature. Performing electrostatic spinning on the obtained product to obtain functionalized UiO-66-NH2The composite membrane is named as TPU/0.1 THB/U6N-1.25.
Example 4 functionalized UIO-66-NH2Composite membrane (TPU/0.1THB/U6N-2.0)
The steps (A) and (B) are the same as those (A) and (B) in example 1
(III) functionalized UIO-66-NH2Preparation of composite film (TPU/0.1THB/U6N-2.0)
1.5g of polyurethane particles are weighed out and mixed with a mixed solution of 5mL of dimethylformamide and 5mL of tetrahydrofuran and stirred thoroughly at 323K for 6 h. 2.0g of 0.1THB/U6N were then added to the suspension and stirred at 323K for 1h, followed by 12h sonication at room temperature and 3h stirring at room temperature. Performing electrostatic spinning on the obtained product to obtain functionalized UiO-66-NH2The composite membrane is named as TPU/0.1 THB/U6N-2.0.
Example 5 detection
The SEM of TPU, TPU/0.1THB/U6N-0.75, TPU/0.1THB/U6N-1.25, TPU/0.1THB/U6N-1.5 and TPU/0.1THB/U6N-2.0 are shown in FIG. 2. As can be seen from FIG. 2, with increasing addition of 0.1THB/U6N, the larger the exposed active sites, the smaller the diameter of the nanofibers in electrospinning. Although M is functionalized in THBOFs at 2.0g, the most active sites were exposed, but the nanofibers broke to render the functionalized UiO-66-NH2The flexibility of the composite film is reduced.
FIG. 3 is a representation of the TPU, TPU/0.1THB/U6N-1.5 and 0.1THB/U6NFT-IR spectra. As can be seen from FIG. 3, the ratio of TPU/0.1THB/U6N-1.5 is 3347cm-1And 2975cm-1The characteristic infrared peak of (A) is attributed to-NH of the TPU2A stretching vibration peak. -CH2-and-CH3Has a peak of expansion and contraction of 1599cm-1And 1120cm-1The characteristic infrared peak of (A) is attributed to-NH on TPU/0.1THB/U6N-1.52Characteristic stretching vibration peak of (2). The above results demonstrate the successful combination of THB functionalized metal organic frameworks and polyurethanes.
Example 2 Effect of acidity on the ability of TPU/0.1THB/U6N-1.5 to adsorb Ga (III)
The method comprises the following steps: separately, 20mg of the TPU prepared in example 1/0.1 THB/U6N-1.5 were weighed out and added to 10mL of a solution having a concentration of 20 mg. L-1In the gallium solution, the pH of the solution was adjusted to 1, 2, 3, 10, the adsorption equilibrium was oscillated in an oscillation tank at 30 ℃ and 180r/min, and the concentration of gallium ions in the adsorbed solution was measured, the results are shown in FIG. 4.
As can be seen from fig. 4, as the pH increases, the adsorption performance increases. The optimal acidity of the TPU/0.1THB/U6N-1.5 composite membrane is the same as that of the functionalized metal organic framework material 0.1 THB/U6N. The polyurethane has almost no adsorption effect on gallium ions, and the adsorption effect can reach about 80% after the polyurethane and the functionalized metal organic framework 0.1THB/U6N are compounded to form the composite membrane.
Effect of comparative example acidity on the Ga (III) adsorption Properties of THB functionalized U6N
The method comprises the following steps: 0.05 g, 0.10 g, 0.25 g, 0.50g of 3,4, 5-Trihydroxybenzaldehyde (THB) and 0.5g of UiO-66-NH were weighed out separately2(U6N) was mixed into a 50mL three-necked flask. Subsequently, 25mL of absolute ethanol was added and reacted at 343K for 24h, and then the resultant was washed several times with absolute ethanol and distilled water, and after drying at 343K for 12h, the final products were obtained, named 0.05THB/U6N, 0.1THB/U6N, 0.25THB/U6N, 0.50 THB/U6N. Respectively weighing 20mg of the above prepared 0.05THB/U6N, 0.1THB/U6N, 0.25THB/U6N and 0.50THB/U6N, and adding into 10mL of concentrated solutionDegree of 20 mg.L-1In the gallium solution, the pH of the solution was adjusted to 1, 2, 3, 10, the adsorption equilibrium was oscillated in an oscillation tank at 30 ℃ and 180r/min, and the concentration of gallium ions in the adsorbed solution was measured, the results are shown in FIG. 5.
As shown in fig. 5. The adsorption effect of xTHB/U6N on gallium is generally better than that of U6N, and the adsorption effect of 0.1THB/U6N on gallium is optimal. The adsorption effect is more pronounced with a progressive reduction in acidity, the effect being optimal at alkaline pH up to 10.
Example 3 adsorption isotherm of TPU/0.1THB/U6N-1.5 composite films on Ga (III)
The method comprises the following steps: the preparation concentration is 20 mg.L-1，40mg·L-1，60mg·L-1，80mg·L-1，100mg·L-1，120mg·L-1Respectively weighing 20mg of TPU/0.1THB/U6N-1.5 prepared in example 1, and adding the weighed materials into the prepared 20mL solution, wherein the concentration of the solution is 20-120 mg.L-1The pH of the gallium solution is 10, and the gallium solution is oscillated and adsorbed in an oscillating box at 30 ℃ and 180r/min for equilibrium. The results are shown in FIG. 6.
As shown in FIG. 6, the adsorption curve followed the Langmuir isothermal adsorption model, indicating that Ga (III) was adsorbed as a monolayer on the surface of TPU/0.1 THB/U6N-1.5. The saturated adsorption capacity of TPU/0.1THB/U6N-1.5 to Ga (III) is 96.18mg g-1。
Example 4 concentration of Metal ions vs. functionalized UiO-66-NH2Influence of composite membrane on water flux and adsorption performance
The method comprises the following steps: the preparation concentration is 10 mg.L-1，20mg·L-1，30mg·L-1，40mg·L-1，50mg·L-11000mL of the gallium ion solution was filtered through a filter membrane of TPU/0.1THB/U6N-1.5, and the water flux was measured by observing the amount pumped in one hour, as shown in FIG. 7 (A). 20mg of the TPU prepared in example 1/0.1 THB/U6N-1.5 were weighed out and added to the above prepared 20mL of 10-50 mg. L-1The solution of gallium (2) was adjusted to pH 10, and the adsorption equilibrium was oscillated at 30 ℃ and 180r/min in a shaking chamber to measure the residual ion concentration, as shown in FIG. 7 (B).
As shown in FIG. 7, the adsorption capacity of the composite film for gallium increased with the concentration of gallium ionsLarge gradually increases, but the water flux gradually decreases. From the above results, it is found that the concentration of gallium ions is responsible for the functionalization of UiO-66-NH2The water flux of the composite film is reduced, but the good gallium adsorption effect can be still maintained.
Example 5 temperature vs. functionalized UiO-66-NH2Influence of composite membrane on water flux and adsorption performance
The method comprises the following steps: the preparation concentration is 20 mg.L-1The gallium ion solution was extracted with 1000mL of the solution at 20 ℃, 30 ℃, 40 ℃, 50 ℃ using TPU/0.1THB/U6N-1.5 as a filter membrane, the amount of water pumped for one hour was observed, and the water flux was measured, as shown in FIG. 8 (A). 20mg of the TPU prepared in example 1/0.1 THB/U6N-1.5 were each weighed out and added to the above-prepared 20mL of 20 mg. L-1The gallium solution (2) was subjected to equilibrium adsorption by oscillation at a pH of 10 in an oscillation tank at 20 ℃, 30 ℃, 40 ℃, 50 ℃ and 180r/min, and the residual ion concentration was measured, as shown in FIG. 8 (B).
As can be seen from FIG. 8, the water flux slightly increased as the temperature increased from 20 ℃ to 50 ℃ but the adsorption rate for Ga (III) slightly decreased. Although temperature vs. functionalized UiO-66-NH2The water flux and the gallium adsorption rate of the composite membrane are influenced, but the composite membrane can still maintain good water flux and good adsorption performance.
Example 6 time-Pair functionalized UiO-66-NH2Influence of composite membrane water flux and adsorption Properties
The method comprises the following steps: the preparation concentration is 20 mg.L-1Taking 1000mL of the gallium ion solution, performing suction filtration by using TPU/0.1THB/U6N-1.5 as a filter membrane, observing the water pumping amount for 24 hours, and measuring the water flux as shown in figure 9 (A). 20mg of the TPU prepared in example 1/0.1 THB/U6N-1.5 were each weighed out and added to the above-prepared 20mL of 20 mg. L-1The solution of gallium (2) was adsorbed by shaking in a shaking chamber at 30 ℃ and 180r/min with the pH of the solution being 10, and the residual ion concentration was measured every 1 hour for 24 hours, as shown in FIG. 9 (B).
As shown in fig. 9. The TPU/0.1THB/U6N-1.5 membrane maintained excellent water flux over 12h, after which the water flux began to drop. During the dynamic adsorption process for a long time, the recovery performance of TPU/0.1THB/U6N-1.5 to Ga (III) is gradually improved within 12h, and the recovery performance reaches the balance at 10h and then keeps stable. The results show that the metal organic framework composite membrane with long-term suction filtration still has better water flux and gallium adsorption effect.
Example 7 functionalized UiO-66-NH2Elution-cycle performance of composite membranes
The method comprises the following steps: the preparation concentration is 20 mg.L-120mg of the TPU/0.1THB/U6N-1.5 prepared in example 1 are weighed respectively and added into the prepared 20mL of gallium ion solution with the concentration of 20 mg.L-1The gallium solution is oscillated in an oscillation box to carry out adsorption equilibrium, and the concentration of the residual ions is measured. With 0.2, 0.4, 0.8, 1.0, 2.0 and 3.0mol L-1As eluent, HCl was used for the elution experiments. A suitable eluent was selected for the cyclic elution experiment as shown in figure 10.
From Table 1, the TPU/0.1THB/U6N-1.5 used 2.0 and 3.0mol L-1The elution rate of hydrochloric acid elution can reach more than 95 percent, and 2.0mol L is selected for protecting the environment-1Hydrochloric acid is the eluent TPU/0.1 THB/U6N-1.5. As shown in FIG. 10, after 5 times of cyclic elution experiments, the adsorption effect of TPU/0.1THB/U6N-1.5 on Ga (III) still reaches about 90%, and the results prove that the adsorption cycle performance is good.
TABLE 1 elution rates of different concentrations of hydrochloric acid solutions on TPU/0.1THB/U6N-1.5 for adsorption of Ga (III)
Figure GDA0003630874350000071

Claims (8)

1. Functionalized UIO-66-NH2The application of the composite membrane in gallium adsorption is characterized in that the method comprises the following steps: weighing functionalized UIO-66-NH2Mixing the composite membrane 20-25mg with gallium solutions with different acidity, vibrating, balancing, measuring the concentration of gallium ions in the adsorbed solution, and eluting with an eluent;
the functionalized UIO-66-NH2The preparation method of the composite membrane comprises the following steps:
1) sequentially adding UiO-66-NH2And 3,4, 5-trihydroxybenzaldehyde into a three-neck flaskThen adding absolute ethyl alcohol, reacting for 22-27h under 333-2；
2) Mixing the polyurethane particles with a mixed solution of dimethylformamide and tetrahydrofuran and fully stirring for 5-8h at 313-333K, and then, adding the functionalized UiO-66-NH2Adding the material into the suspension, stirring for 1-3h under the condition of 313-333K, then carrying out ultrasonic treatment for 10-15h at room temperature, stirring for 3-5h at room temperature, and carrying out electrostatic spinning on the obtained product to obtain the functionalized UiO-66-NH2A composite membrane.
2. The use of claim 1, wherein said UiO-66-NH is2The preparation method comprises the following steps: dissolving zirconium tetrachloride and ligand 2-amino terephthalic acid in a mixed solution of dimethylformamide and concentrated hydrochloric acid, fully stirring for 2-5h at room temperature, transferring to a polytetrafluoroethylene reaction kettle, reacting for 22-27h at 383-2。
3. The use according to claim 2, wherein concentrated hydrochloric acid to dimethylformamide = 1: 13-15 by volume in the mixed solution.
4. Use according to claim 1, characterized in that in step 1), UiO-66-NH is added in a mass ratio23,4, 5-trihydroxybenzaldehyde = 1: 0.1-1.
5. The use according to claim 1, wherein in step 2), the polyurethane particles are mixed in a mass ratio of: functionalized UiO-66-NH2Material = 1: 0.5-1.3.
6. Use according to claim 1, characterized in that the conditions under which the electrospinning is carried out are: spinning at 25-30 deg.C, humidity of 75-80%, and injection speed of 10-12 μ L/min, and collecting the membrane on tinfoil paper or filter paper.
7. Use according to claim 1, wherein the gallium solution has a pH =3 or 10.
8. The use according to claim 1, wherein the eluent is HCl, and the HCl concentration is greater than 1 mol/L.
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